U.S. patent application number 14/481035 was filed with the patent office on 2015-03-19 for phosphoric ester preparations with reduced hygroscopicity.
The applicant listed for this patent is LANXESS Deutschland GmbH. Invention is credited to Jan-Gerd HANSEL, Heiko TEBBE.
Application Number | 20150080276 14/481035 |
Document ID | / |
Family ID | 49162042 |
Filed Date | 2015-03-19 |
United States Patent
Application |
20150080276 |
Kind Code |
A1 |
HANSEL; Jan-Gerd ; et
al. |
March 19, 2015 |
PHOSPHORIC ESTER PREPARATIONS WITH REDUCED HYGROSCOPICITY
Abstract
The present invention relates to phosphoric ester preparations
with reduced hygroscopicity, to use of these as flame retardants
and hydraulic fluids, and to polyurethanes which comprise the
phosphoric ester preparations of the invention.
Inventors: |
HANSEL; Jan-Gerd; (Bergisch
Gladbach, DE) ; TEBBE; Heiko; (Dormagen, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
LANXESS Deutschland GmbH |
Cologne |
|
DE |
|
|
Family ID: |
49162042 |
Appl. No.: |
14/481035 |
Filed: |
September 9, 2014 |
Current U.S.
Class: |
507/238 ;
252/609; 521/107; 521/163; 524/141 |
Current CPC
Class: |
C08G 18/7621 20130101;
C09K 8/62 20130101; C08G 18/48 20130101; C08G 2101/0008 20130101;
C08K 5/521 20130101; C10M 105/74 20130101; C10N 2030/66 20200501;
C08K 5/0066 20130101; C08G 18/42 20130101; C08G 18/14 20130101;
C08G 65/3353 20130101; C10N 2040/08 20130101; C10M 2223/04
20130101; C10M 2223/0405 20130101; C08K 5/523 20130101; C09K 21/14
20130101 |
Class at
Publication: |
507/238 ;
252/609; 524/141; 521/163; 521/107 |
International
Class: |
C08K 5/521 20060101
C08K005/521; C09K 8/62 20060101 C09K008/62; C08G 18/08 20060101
C08G018/08; C08G 18/76 20060101 C08G018/76; C08G 18/48 20060101
C08G018/48; C08G 18/42 20060101 C08G018/42; C09K 21/14 20060101
C09K021/14; C08K 5/523 20060101 C08K005/523 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 13, 2013 |
EP |
13184290.8 |
Claims
1. A phosphoric ester preparation which comprises i) an oligomer
mixture a) comprising at least three poly(alkylene phosphates)
corresponding to the formula (I) ##STR00016## in which R.sup.1,
R.sup.2, R.sup.3 and R.sup.4 are respectively mutually
independently a straight-chain or branched C.sub.1- to
C.sub.8-alkyl moiety or a straight-chain or branched C.sub.1- to
C.sub.4-alkoxyethyl moiety, A is a straight-chain, branched and/or
cyclic C.sub.4- to C.sub.20-alkylene moiety, or A is a moiety of
the formula --CH.sub.2--CH.dbd.CH--CH.sub.2--, a moiety of the
formula --CH.sub.2--C.ident.C--CH.sub.2--, a moiety of the formula
--CHR.sup.5--CHR.sup.6--(O--CHR.sup.7--CHR.sup.8).sub.a--, a moiety
of the formula
--CHR.sup.5--CHR.sup.6--S(O).sub.b--CHR.sup.7--CHR.sup.8-- or a
moiety of the formula
--(CHR.sup.5--CHR.sup.6--O).sub.c--R.sup.9--(O--CHR.sup.7--CHR.sup.8).sub-
.d--, in which a is an integer from 1 to 5, b is an integer from 0
to 2, c and d are mutually independently an integer from 1 to 5,
R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are mutually independently H
or methyl, R.sup.9 is a moiety of the formula
--CH.sub.2--CH.dbd.CH--CH.sub.2--, a moiety of the formula
--CH.sub.2--C.ident.C--CH.sub.2--, a 1,2-phenylene moiety, a
1,3-phenylene moiety, a 1,4-phenylene moiety, or a moiety of the
formula (II) ##STR00017## a moiety of the formula (III)
##STR00018## a moiety of the formula (IV) ##STR00019## or a moiety
of the formula --C(.dbd.O)--R.sup.12--C(O)--, where R.sup.10 and
R.sup.11 are respectively mutually independently H or C.sub.1- to
C.sub.4-alkyl or R.sup.10 and R.sup.11 together are an optionally
alkyl-substituted ring having from 4 to 8C atoms, R.sup.12 is a
straight-chain, branched and/or cyclic C.sub.2- to C.sub.8-alkylene
moiety, a 1,2-phenylene moiety, a 1,3-phenylene moiety, or a
1,4-phenylene moiety, and n is an integer from 0 to 100, with the
proviso that the at least three poly(alkylene phosphates) of the
formula (I) differ from one another at least in the number n of the
repeating units, and the average value of the number of the
repeating units n of the at least three poly(alkylene phosphates)
of the formula (I) is greater than L10 and smaller than 2.00, and
ii) at least one phosphoric ester b) with solubility of less than
3.0 g/l in water at 25.degree. C.
2. The phosphoric ester preparations according to claim 1 in which
the oligomer mixture a) comprises at least three poly(alkylene
phosphates) of the formula (I), in which R.sup.1, R.sup.2, R.sup.3
and R.sup.4 are respectively mutually independently a
straight-chain or branched C.sub.1- to C.sub.4-alkyl moiety or a
C.sub.1- or C.sub.2-alkoxyethyl moiety, A is a straight-chain or
branched C.sub.4- to C.sub.10-alkylene moiety, or A is a moiety of
the formula --CH.sub.2--CH.dbd.CH--CH.sub.2--, a moiety of the
formula --CH.sub.2--C.ident.C'CH.sub.2--, a moiety of the formula
--CHR.sup.5--CHR.sup.6--(O--CHR.sup.7--CHR.sup.8).sub.a--, a moiety
of the formula
--CHR.sup.5--CHR.sup.6--S(O).sub.b--CHR.sup.7--CHR.sup.8-- or a
moiety of the formula
--(CHR.sup.5--CHR.sup.6--O).sub.c--R.sup.9--(O--CHR.sup.7--CHR.sup.8).sub-
.d--, in which a is an integer from 1 to 5, b is an integer from 0
to 2, c and d are mutually independently an integer from 1 to 5,
R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are mutually independently H
or methyl, R.sup.9 is a moiety of the formula
--CH.sub.2--CH.dbd.CH--CH.sub.2--, a moiety of the formula
--CH.sub.2--C.ident.C--CH.sub.2--, a 1,2-phenylene moiety, a
1,3-phenylene moiety, a 1,4-phenylene moiety, or a moiety of the
formula (II) ##STR00020## a moiety of the formula (III)
##STR00021## a moiety of the formula (IV) ##STR00022## or a moiety
of the formula --C(O)--R.sup.12--C(.dbd.O)--, where R.sup.10 and
R.sup.11 are respectively mutually independently H or C.sub.1- or
C.sub.2-alkyl, R.sup.12 is a straight-chain or branched C.sub.2- to
C.sub.6-alkylene moiety, a 1,2-phenylene moiety, a 1,3-phenylene
moiety, or a 1,4-phenylene moiety, and n is an integer from 0 to
100.
3. The phosphoric ester preparations according to claim 1 in which
the oligomer mixture a) comprises at least three poly(alkylene
phosphates) of the formula (I) in which R.sup.1, R.sup.2, R.sup.3
and R.sup.4 are respectively mutually independently a
straight-chain or branched C.sub.1- to C.sub.4-alkyl moiety or an
n-butoxyethyl moiety, A is a straight-chain C.sub.4- to
C.sub.6-alkylene moiety, or A is a moiety of the formula
--CH.sub.2--CH.dbd.CH--CH.sub.2--, a moiety of the formula
--CH.sub.2--C.ident.C--CH.sub.2--, a moiety of the formula
--CHR.sup.5--CHR.sup.6--(O--CHR.sup.7--CHR.sup.8).sub.a--, a moiety
of the formula
--CHR.sup.5--CHR.sup.6--S(O).sub.b--CHR.sup.7--CHR.sup.8-- or a
moiety of the formula
--(CHR.sup.5--CHR.sup.6--O).sub.c--R.sup.9--(O--CHR.sup.7--CHR.sup.8).sub-
.d--, in which a is an integer from 1 to 5, b is an integer from 0
to 2, c and d are mutually independently an integer from 1 to 5,
R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are mutually independently H
or methyl, R.sup.9 is a moiety of the formula
--CH.sub.2--CH.dbd.CH--CH.sub.2--, a moiety of the formula
--CH.sub.2--C.ident.C--CH.sub.2--, a 1,2-phenylene moiety, a
1,3-phenylene moiety, a 1,4-phenylene moiety, or a moiety of the
formula (II) ##STR00023## a moiety of the formula (III)
##STR00024## a moiety of the formula (IV) ##STR00025## or a moiety
of the formula --C(.dbd.O)--R.sup.12--C(.dbd.O)--, where R.sup.10
and R.sup.11 are respectively mutually independently H or C.sub.1-
or C.sub.2-alkyl, R.sup.12 is a straight-chain or branched C.sub.2-
to C.sub.6-alkylene moiety, a 1,2-phenylene moiety, a 1,3-phenylene
moiety, or a 1,4-phenylene moiety, and n is an integer from 0 to
100.
4. The phosphoric ester preparations according to claim 1 in which
the oligomer mixture a) comprises at least three poly(alkylene
phosphates) of the formula (I) in which R.sup.1, R.sup.2, R.sup.3
and R.sup.4 are identical and are ethyl, n-propyl, isopropyl,
n-butyl, isobutyl or n-butoxyethyl, A is a straight-chain C.sub.4-
to C.sub.6-alkylene moiety, or A is a moiety of the formulae
##STR00026## A is a moiety
--CHR.sup.5--CHR.sup.6--(O--CHR.sup.7--CHR.sup.8).sub.a--, in which
a is an integer from 1 to 2 and R.sup.5, R.sup.6, R.sup.7 and
R.sup.8 are identical and are H, or is a moiety
--(CHR.sup.5--CHR.sup.6--O).sub.c--R.sup.9--(O--CHR.sup.7--CHR.sup.8).sub-
.d--, in which c and d are mutually independently an integer from 1
to 2, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are identical and are
H, R.sup.9 is a moiety of the formula (II), where R.sup.10 and
R.sup.11 are identical and are methyl, and n is an integer from 0
to 20.
5. The phosphoric ester preparations according to claim 1 in which
the phosphoric esters b) correspond to the formula (VIII)
##STR00027## in which R.sup.13, R.sup.14, R.sup.15 and R.sup.16 are
respectively mutually independently straight-chain or branched
C.sub.4- to C.sub.12-alkyl, C.sub.4- to C.sub.12-alkoxyalkyl,
C.sub.3- to C.sub.12-chloroalkyl, C.sub.3- to
C.sub.12-dichloroalkyl or optionally mono- or poly-C.sub.1- to
C.sub.4-alkyl-substituted C.sub.6- to C.sub.10-aryl, X is a
C.sub.4- to C.sub.8-alkylene moiety, a 1,2-phenylene moiety, a
1,3-phenylene moiety, a 1,4-phenylene moiety or a moiety of the
formula (II), ##STR00028## in which R.sup.10 and R.sup.11 are
defined as in claim 1, and m is 0 or 1.
6. The phosphoric ester preparations according to claim 1 in which
the phosphoric esters b) are selected from the group of triphenyl
phosphate, diphenyl cresyl phosphate, tricresyl phosphate,
isopropylated or butylated aryl phosphates, bisphenol A
bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate),
hydroquinone bis(diphenyl phosphate), neopentyl glycol bis(d(phenyl
phosphate), triisobutyl phosphate, tributoxyethyl phosphate,
tris(chloroisopropyl)phosphate and
tris(dichloropropyl)phosphate.
7. The phosphoric ester preparation according to claim 1 in which
the materials are liquids with dynamic viscosity from 20 to 5000
mPas at 23.degree. C.
8. The phosphoric ester preparation according to claim 1 in which
comprises from 30 to 70% by weight, preferably from 40 to 60% by
weight, of the oligomer mixture a) and from 30 to 70% by weight,
preferably from 40 to 60% by weight, of at least one phosphoric
ester b), based on the entire preparation.
9. The phosphoric ester preparation according to claim 1 in which
comprises one or more auxiliaries selected from the group of the
solvents, antioxidants, stabilizers and colorants.
10. A process for the production of the phosphoric ester
preparation according to claim 1 in which in oligomer mixture a)
according to claim 1 and at least one phosphoric ester b) according
to claim 1 are mixed with one another optionally in the presence of
one or more auxiliaries.
11. The use of the phosphoric ester preparation according to claim
1 as flame retardant.
12. The use according to claim 11 in which the phosphoric ester
preparation is used as flame retardant for polyurethanes.
13. The use according to claim 12 in which the polyurethanes are
foams, preferably flexible polyurethane foams based on polyether
polyols or on polyester polyols.
14. A flame retardant preparation comprising at least one
phosphoric ester preparation according to claim 1, one or more
flame retardants different from the phosphoric ester preparation
and optionally one or more auxiliaries.
15. A polyurethane comprising a phosphoric ester preparation
according to at least one of claim 1.
16. A polyurethane foam, preferably a flexible polyurethane foams
based on polyether polyols or on polyester polyols, comprising a
phosphoric ester preparation according to claim 1.
17. A process for the production of a polyurethane according to
claim 15 in which organic polyisocyanates are reacted, in the
presence of a phosphoric ester composition according to at least
one of claim 1 and in the presence of conventional blowing agents,
stabilizers, activators and/or other conventional auxiliaries and
additives, at a temperature from 20 to 80.degree. C., with
compounds having at least 2 hydrogen atoms reactive towards
isocyanates.
18. The process according to claim 17 in which the quantity used of
the phosphoric ester preparation is from 0.5 to 30 parts by weight,
preferably from 3 to 25 parts by weight, based on 100 parts by
weight of polyol component.
19. The use of the polyurethanes according to claim 15 in furniture
cushioning, textile inlays, mattresses, vehicle seats, armrests,
components, seat cladding and dashboard cladding, cable sheathing,
gaskets, coatings, lacquers, adhesives, adhesion promoters and
fibres.
20. A hydraulic fluid comprising a phosphoric ester preparation
according to claim 1.
21. A process for reducing the hygroscopicity of poly(alkylene
phosphates i) in which the poly(alkylene phosphate) is combined
with from 40 to 230% by weight, based on the mass of the
poly(alkylene phosphate), at least one phosphoric ester with
solubility of less than 3.0 g/l in water at 25.degree. C., and the
mixture is homogenized.
22. The process according to claim 21 in which the poly(alkylene
phosphates) are an oligomer mixture a) according to claim 1.
Description
[0001] The present invention relates to phosphoric ester
preparations with reduced hygroscopicity, to a method for
production thereof and to use of these as flame retardants and
hydraulic fluids, and also to polyurethanes which comprise the
phosphoric ester preparations of the invention.
DESCRIPTION OF THE PRIOR ART
[0002] Poly(alkylene phosphates) can be used in various technical
applications, for example as lubricants (cf. U.S. Pat. No.
2,632,767), hydraulic fluids (cf. U.S. Pat. No. 4,056,480),
plasticizers (cf. U.S. Pat. No. 2,782,128) and as flame retardants
(cf. EP 1 746 129 B1, and the European Patent Application No.
12177287.5 which is not a prior publication).
[0003] However, a problematic factor in those applications is that
the poly(alkylene phosphates) are distinctly hygroscopic, see
Example M-CE1. Hygroscopicity is the term used for the property
that causes a substance to absorb water from the water vapour
present in air. This process causes an uncontrolled rise in the
water content of the poly(alkylene phosphates), and this can lead
to difficulties in the applications mentioned: the increased water
content in hydraulic fluids can lead to the formation of vapour
bubbles which can cause undesired compressibility. Flame retardants
with undesired water content can cause hydrolysis of the matrix
that is to be protected (for example a plastic). In the case of
production of polyurethanes, water content in the flame retardants
used is always undesired, since it leads to uncontrolled foaming.
Even in the case of water-blown polyurethane foams, all of the raw
materials should have minimal and constant water content, in order
that the properties of the foam can be adjusted in a controlled
manner via the exact quantity added of water as blowing agent. In
general terms, increased water content can promote the corrosion of
metallic materials.
[0004] For these reasons, the use of poly(alkylene phosphates)
coupled with protective measures which must prevent contact of the
product with humid air along the entire product pathway. By way of
example, storage tanks have to be blanketed with inert gas. This
increases technical cost.
[0005] WO 2001/018088 A1 describes mixtures of oligomeric
poly(alkylene phosphates) and non-oligomeric, non-halogenated
organophosphorus flame retardants. However, WO 2001/018088 A1 does
not address the hygroscopicity problem. WO 2001/018088 A1 gives
particular preference to mixtures based on what is known as
poly(ethyl ethyleneoxy) phosphate,
EtO-[P(.dbd.O)OEt-CH.sub.2CH.sub.2--].sub.n--P(.dbd.O)(OEt).sub.2,
where the average value of the number of the repeating units n is
from 2 to 20. Poly(ethyl ethyleneoxy)phosphate is marketed by way
of example as Fyrol.RTM. PNX by ICL-IP. These mixtures based on
poly(ethyl ethyleneoxy)phosphate are described in WO 2001/018088 A1
as flame retardants for polyurethane foams, but feature a
considerable disadvantage: that they although they can be
successfully processed with polyether polyols they cannot be
successfully processed with polyester polyols (see Examples).
[0006] It was therefore an object of the present invention to
provide products which are based on poly(alkylene phosphates) and
which feature reduced hygroscopicity, and which have good
processability in polyester polyols.
[0007] The said object is achieved via mixtures which comprise
certain phosphoric esters alongside an oligomer mixture of
poly(alkylene phosphates).
SUMMARY OF THE INVENTION
[0008] The present invention therefore provides phosphoric ester
preparations characterized in that they comprise [0009] an oligomer
mixture a) comprising at least three poly(alkylene phosphates)
corresponding to the formula (I)
[0009] ##STR00001## [0010] in which [0011] R.sup.1, R.sup.2,
R.sup.3 and R.sup.4 are respectively mutually independently a
straight-chain or branched C.sub.1- to C.sub.8-alkyl moiety or a
straight-chain or branched C.sub.1- to C.sub.4-alkoxyethyl moiety,
[0012] A is a straight-chain, branched and/or cyclic C.sub.4- to
C.sub.20-alkylene moiety, or [0013] A is a moiety of the formula
--CH.sub.2--CH.dbd.CH--CH.sub.2--, a moiety of the formula
--CH.sub.2--C.ident.C--CH.sub.2--, a moiety of the formula
--CHR.sup.5--CHR.sup.6--(O--CHR.sup.7--CHR.sup.8).sub.a--, a moiety
of the formula
--CHR.sup.5--CHR.sup.6--S(O).sub.b--CHR.sup.7--CHR.sup.8-- or a
moiety of the formula
--(CHR.sup.5--CHR.sup.6--O).sub.c--R.sup.9--(O--CHR.sup.7--CHR.sup.8).sub-
.d--, [0014] in which [0015] a is an integer from 1 to 5, [0016] b
is an integer from 0 to 2, [0017] c and d are mutually
independently an integer from 1 to 5, [0018] R.sup.5, R.sup.6,
R.sup.7 and R.sup.8 are mutually independently H or methyl,
[0019] R.sup.9 is a moiety of the formula
--CH.sub.2--CH.dbd.CH--CH.sub.2--, a moiety of the formula
--CH.sub.2--C.ident.C--CH.sub.2--, a 1,2-phenylene moiety, a
1,3-phenylene moiety, a 1,4-phenylene moiety, or a moiety of the
formula (II)
##STR00002## [0020] a moiety of the formula (III)
[0020] ##STR00003## [0021] a moiety of the formula (IV)
[0021] ##STR00004## [0022] or a moiety of the formula
--C(.dbd.O)--R.sup.12--C(.dbd.O)--, [0023] where [0024] R.sup.10
and R.sup.11 are respectively mutually independently H or C.sub.1-
to C.sub.4-alkyl or R.sup.10 and R.sup.11 together are an
optionally alkyl-substituted ring having from 4 to 8 C atoms,
[0025] R.sup.12 is a straight-chain, branched and/or cyclic to
C.sub.8-alkylene moiety, a 1,2-phenylene moiety, a 1,3-phenylene
moiety, or a 1,4-phenylene moiety, and [0026] n is an integer from
0 to 100, [0027] with the proviso that the at least three
poly(alkylene polyphosphates) of the formula (I) differ from one
another at least in the number n of the repeating units, and [0028]
the average value of the number of the repeating units n of the at
least three poly(alkylene phosphates) of the formula (I) is greater
than 1.10 and smaller than 2.00, [0029] and [0030] at least one
phosphoric ester b) with solubility of less than 3.0 g/l in water
at 25.degree. C.
DETAILED DESCRIPTION OF THE INVENTION
[0031] Preference is given to poly(alkylene phosphates) of the
formula (I) in which R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
identical and are either ethyl, n-propyl, isopropyl, n-butyl,
isobutyl or n-butoxyethyl. It is preferable that A in formula (I)
is a straight-chain C.sub.4- to C.sub.6-alkylene moiety.
[0032] Preference is further given to poly(alkylene phosphates) of
the formula (I) in which A is a moiety of the formula (II), in
which R.sup.10 and R.sup.11 are identical and are methyl, or is a
moiety of the formulae (V), (VI) or (VII),
##STR00005##
[0033] Preference is likewise given to poly(alkylene phosphates) of
the formula (I) in which A is a moiety of the formula
--CHR.sup.5--CHR.sup.6--(O--CHR.sup.7--CHR.sup.8).sub.a--, in which
a is a number from 1 to 2 and R.sup.5, R.sup.6, R.sup.7 and R.sup.8
are identical and are H or is a moiety of the formula
--(CHR.sup.5--CHR.sup.6--O).sub.c--R.sup.9--(O--CHR.sup.7--CHR.sup.8).sub-
.d--, in which c and d are mutually independently an integer from 1
to 2, and R.sup.9 is a moiety of the formula (II), where R.sup.10
and R.sup.11 are identical and are methyl.
[0034] Preference is given to phosphoric ester preparations of the
invention which comprise an oligomer mixture a) comprising at least
three poly(alkylene phosphates) of the formula (I), [0035] in which
[0036] R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are respectively
mutually independently a straight-chain or branched C.sub.1- to
C.sub.4-alkyl moiety or a C.sub.1- or C.sub.2-alkoxyethyl moiety,
[0037] A is a straight-chain or branched C.sub.4- to
C.sub.10-alkylene moiety, or [0038] A is a moiety of the formula
--CH.sub.2--CH.dbd.CH--CH.sub.2--, a moiety of the formula
--CH.sub.2--C.ident.C--CH.sub.2--, a moiety of the formula
--CHR.sup.5--CHR.sup.6--(O--CHR.sup.7--CHR.sup.8).sub.a--, a moiety
of the formula
--CHR.sup.5--CHR.sup.6--S(O).sub.b--CHR.sup.7--CHR.sup.8-- or a
moiety of the formula
--(CHR.sup.5--CHR.sup.6--O).sub.c--R.sup.9--(O--CHR.sup.7--CHR.sup.8).sub-
.d--, [0039] in which [0040] a is an integer from 1 to 5, [0041] b
is an integer from 0 to 2, [0042] c and d are mutually
independently an integer from 1 to 5, [0043] R.sup.5, R.sup.6,
R.sup.7 and R.sup.8 are mutually independently H or methyl, [0044]
R.sup.9 is a moiety of the formula
--CH.sub.2--CH.dbd.CH--CH.sub.2--, a moiety of the formula
--CH.sub.2--C.ident.C--CH.sub.2--, a 1,2-phenylene moiety, a
1,3-phenylene moiety, a 1,4-phenylene moiety, or a moiety of the
formula (II)
[0044] ##STR00006## [0045] a moiety of the formula (III)
[0045] ##STR00007## [0046] a moiety of the formula (IV)
[0046] ##STR00008## [0047] or a moiety of the formula
--C(.dbd.O)--R.sup.12--C(.dbd.O)--, [0048] where [0049] R.sup.10
and R.sup.11 are respectively mutually independently H or C.sub.1-
or C.sub.2-alkyl, [0050] R.sup.12 is a straight-chain or branched
C.sub.2- to C.sub.6-alkylene moiety, a 1,2-phenylene moiety, a
1,3-phenylene moiety, or a 1,4-phenylene moiety, and [0051] n is an
integer from 0 to 100.
[0052] Very particular preference is given to phosphoric ester
preparations of the invention which comprise an oligomer mixture a)
comprising at least three poly(alkylene phosphates) of the formula
(I) [0053] in which [0054] R.sup.1, R.sup.2, R.sup.3 and R.sup.4
are respectively mutually independently a straight-chain or
branched C.sub.1- to C.sub.4-alkyl moiety or an n-butoxyethyl
moiety, [0055] A is a straight-chain C.sub.4- to C.sub.6-alkylene
moiety, or [0056] A is a moiety of the formula
--CH.sub.2--CH.dbd.CH--CH.sub.2--, a moiety of the formula
--CH.sub.2--C.ident.C--CH.sub.2--, a moiety of the formula
--CHR.sup.5--CHR.sup.6--(O--CHR.sup.7--CHR.sup.8).sub.a--, a moiety
of the formula
--CHR.sup.5--CHR.sup.6--S(O).sub.b--CHR.sup.7--CHR.sup.8-- or a
moiety of the formula
--(CHR.sup.5--CHR.sup.6--O).sub.c--R.sup.9--(O--CHR.sup.7--CHR.sup.8).sub-
.d--, [0057] in which [0058] a is an integer from 1 to 5, [0059] b
is an integer from 0 to 2, [0060] c and d are mutually
independently an integer from 1 to 5, [0061] R.sup.5, R.sup.6,
R.sup.7 and R.sup.8 are mutually independently H or methyl, [0062]
R.sup.9 is a moiety of the formula
--CH.sub.2--CH.dbd.CH--CH.sub.2--, a moiety of the formula
--CH.sub.2--C.ident.C--CH.sub.2--, a 1,2-phenylene moiety, a
1,3-phenylene moiety, a 1,4-phenylene moiety, or a moiety of the
formula (II)
[0062] ##STR00009## [0063] a moiety of the formula (III)
[0063] ##STR00010## [0064] a moiety of the formula (IV)
[0064] ##STR00011## [0065] or a moiety of the formula
--C(.dbd.O)--R.sup.12--C(.dbd.O)--, [0066] where [0067] R.sup.10
and R.sup.11 are respectively mutually independently H or C.sub.1-
or C.sub.2-alkyl, [0068] R.sup.12 is a straight-chain or branched
C.sub.2- to C.sub.6-alkylene moiety, a 1,2-phenylene moiety, a
1,3-phenylene moiety, or a 1,4-phenylene moiety, and [0069] n is an
integer from 0 to 100.
[0070] Preference is in particular given to phosphoric ester
preparations of the invention which comprise an oligomer mixture a)
comprising at least three poly(alkylene phosphates) of the formula
(I) [0071] in which [0072] R.sup.1, R.sup.2, R.sup.3 and R.sup.4
are identical and are ethyl, n-propyl, isopropyl, n-butyl, isohutyl
or n-butoxyethyl, [0073] A is a straight-chain C.sub.4- to
C.sub.6-alkylene moiety, or [0074] A is a moiety of the
formulae
[0074] ##STR00012## [0075] or [0076] A is a moiety
--CHR.sup.5--CHR.sup.6--(O--CHR.sup.7--CHR.sup.8).sub.a--, in which
a is an integer from 1 to 2 and R.sup.5, R.sup.6, R.sup.7 and
R.sup.8 are identical and are H, or is a moiety
--(CHR.sup.5--CHR.sup.6--O).sub.c--R.sup.9--(O--CHR.sup.7--CHR.sup.8).sub-
.d--, in which c and d are mutually independently an integer from 1
to 2, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are identical and are
H, R.sup.9 is a moiety of the formula (II), where R.sup.10 and
R.sup.11 are identical and are methyl, [0077] and [0078] n is an
integer from 0 to 20.
[0079] It is preferable that the oligomer mixtures a) present in
the phosphoric ester preparations of the invention and the
poly(alkylene phosphates) present therein are halogen-free. For the
purposes of the present invention, the expression "halogen-free"
means that the poly(alkylene phosphates) of the formula (I) do not
comprise the elements fluorine, chlorine, bromine and/or iodine and
that the oligomer mixtures a) present in the phosphoric ester
preparations of the invention do not comprise any other substances
in a quantity that causes content of one or more of the elements
fluorine, chlorine, bromine and iodine to be greater than 5000 ppm,
based on the oligomer mixture a).
[0080] The oligomer mixtures a) present in the phosphoric ester
preparations of the invention comprise at least three, preferably
more than three different poly(alkylene phosphates) of the general
formula (I) which differ from one another at least in the number n
of the repeating units and thus in their molar mass. The person
skilled in the art uses suitable average values to describe
oligomer mixtures of this type, for example the number-average
molar mass M.sub.n and the average value of the number of the
repeating units n in the molecules of the formula (I) present in
the oligomer mixture.
[0081] The number-average molar mass M.sub.n of the poly(alkylene
phosphates) of the formula (I) present in the oligomer mixture a)
in the invention is determined via gel permeation chromatography
with tetrahydrofuran as eluent against polystyrene standards. This
method is known to the person skilled in the art, for example from
DIN 55672-1:2007-08. From M.sub.n it is easily possible, by
considering the stoichiometry of the formula (I), to calculate the
average value of the number of the repeating units n in the
poly(alkylene phosphates) present in the oligomer mixture a) (see
Production Example).
[0082] The phosphoric esters b) present in the phosphoric ester
preparations of the invention are preferably esters of
orthophosphoric acid having identically or differently substituted
alkyl, alkylene, alkoxyalkylene, arylalkyl, aryl, arylene or
hetaryl moieties. The materials can also be mixtures of various
esters of the sort frequently encountered in technical products of
this type.
[0083] It is preferable that the phosphoric esters b) are compounds
of the formula (VIII)
##STR00013## [0084] in which [0085] R.sup.13, R.sup.14, R.sup.15
and R.sup.16 are respectively mutually independently straight-chain
or branched C.sub.4- to C.sub.12-alkyl, C.sub.4- to
C.sub.12-alkoxyalkyl, C.sub.3- to C.sub.12-chloroalkyl, C.sub.3- to
C.sub.12-dichloroalkyl or optionally mono- or poly-C.sub.1- to
C.sub.4-alkyl-substituted C.sub.6- to C.sub.10-aryl, [0086] X is a
C.sub.4- to C.sub.8-alkylene moiety, a 1,2-phenylene moiety, a
1,3-phenylene moiety, a 1,4-phenylene moiety or a moiety of the
formula (II),
[0086] ##STR00014## [0087] in which [0088] R.sup.10 and R.sup.11
are as defined above, [0089] and [0090] m is 0 or 1.
[0091] It is particularly preferable that the phosphoric esters b)
are compounds of the formula (VIII) [0092] in which [0093]
R.sup.13, R.sup.14, R.sup.15 and R.sup.16 are mutually
independently optionally mono- or poly-C.sub.1- to
C.sub.4-alkyl-substituted phenyl, [0094] X is a C.sub.4- to
C.sub.8-alkylene moiety, a 1,2-phenylene moiety, a 1,3-phenylene
moiety, a 1,4-phenylene moiety or a moiety of the formula (II),
[0094] ##STR00015## [0095] in which R.sup.10 and R.sup.11 are as
defined above, [0096] and m is 0 or 1.
[0097] Examples of the preferred phosphoric esters b) are triphenyl
phosphate, diphenyl cresyl phosphate, tricresyl phosphate,
isopropylated or butylated aryl phosphates, bisphenol A
bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate),
hydroquinone bis(diphenyl phosphate), neopentyl glycol bis(diphenyl
phosphate), triisobutyl phosphate, tributoxyethyl phosphate,
tris(chloroisopropyl)phosphate and tris(dichloropropyl)phosphate
and mixtures of these.
[0098] The phosphoric esters b) are commercially obtainable
products or can be produced by a known method. It is also possible
to use technical products as phosphoric esters b). It is preferable
here to use those technical products which are termed "neutral"
phosphoric esters, i,e. which have an acid number below 10 mg
KOH/g, preferably below 5.0 mg KOH/g and particularly preferably
below 2.0 mg KOH/g.
[0099] In principle, the oligomer mixtures a) can be produced via
methods known to the person skilled in the art for the production
of alkyl phosphates. By way of example, the oligomer mixtures a)
can be produced via the reaction of alkyl dichlorophosphates of the
formula MO--POCl.sub.2, in which M is a moiety R.sup.1, R.sup.2,
R.sup.3 or R.sup.4 and R.sup.1, R.sup.2, R.sup.3 and R.sup.4 comply
with the general and preferred definitions given above, with
dihydroxy compounds of the formula HO-A-OH, in which A complies
with the general and preferred definitions given above, and with
one or more monohydroxy compounds M-OH, in which M is defined as
above, or via reaction of dihydroxy compounds of the formula
HO-A-OH, in which A complies with the general and preferred
definitions given above, with phosphorus oxychloride POCl.sub.3 and
with one or more monohydroxy compounds M-OH, in which M is a moiety
R.sup.1, R.sup.2, R.sup.3 or R.sup.4, and R.sup.1, R.sup.2, R.sup.3
and R.sup.4 comply with the general and preferred definitions given
above, or via reaction of one or more trialkyl phosphates
(MO).sub.3PO, in which M is as defined above, with phosphorus
pentoxide P.sub.2O.sub.5 and with a cyclic ether.
[0100] Preference is given in the invention to the production
process via reaction of dihydroxy compounds of the formula HO-A-OH,
in which A complies with the general and preferred definitions
given above, with phosphorus oxychloride POCl.sub.3 and with at
least one monohydroxy compound M-OH, in which M is a moiety
R.sup.1, R.sup.2, R.sup.3 or R.sup.4, and R.sup.1, R.sup.2, R.sup.3
and R.sup.4 comply with the general and preferred definitions given
above.
[0101] The present invention further provides a process for the
production of the phosphoric ester preparations of the invention,
characterized in that an oligomer mixture a) complying with the
general or preferred definition given above and at least one
phosphoric ester b) complying with the general or preferred
definition given above are mixed with one another.
[0102] The phosphoric ester preparation of the invention generally
comprises from 30 to 70% by weight, preferably from 40 to 60% by
weight, of oligomer mixture a) and from 30 to 70% by weight,
preferably from 40 to 60% by weight, of at least one phosphoric
ester b), based on the entire preparation.
[0103] It is preferable that the phosphoric ester preparations of
the invention are liquid at about 23.degree. C.
[0104] It is preferable that the viscosity of the phosphoric ester
preparations of the invention is from 20 to 5000 mPas at 23.degree.
C. It is particularly preferable that the viscosity is from 20 to
1000 mPas at 23.degree. C.
[0105] The phosphoric ester preparations of the invention can
preferably comprise, alongside components a) and b), as required by
application sector, one or more auxiliaries, for example from the
group of the solvents, antioxidants, stabilizers and colorants.
Examples of these auxiliaries that can be used are: [0106] solvents
such as alkyl esters of aliphatic or aromatic di- or tricarboxylic
acids, [0107] antioxidants and stabilizers such as sterically
hindered trialkylphenols, alkyl esters of
3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid,
benzofuran-2-ones, secondary aromatic amines, phosphites,
phenothiazines or tocopherols, and [0108] dyes such as soluble
organic colorants, iron oxide pigments or carbon blacks.
[0109] The phosphoric ester preparations of the invention are
suitable for use as flame retardants and for the production of
flame retardant preparations. The present invention further
provides the use of the phosphoric ester preparations of the
invention as flame retardants.
[0110] The phosphoric esters preparations can be used as flame
retardants in any of the applications known to the person skilled
in the art for flame retardants. It is preferable that the
phosphoric ester preparation of the invention is used as flame
retardant for [0111] synthetic polymers such as polyolefins,
polyvinyl chloride, polycarbonates, styrene-based (co)polymers,
polyamides, polyesters, polyurethanes, and thermosets such as epoxy
resins, unsaturated polyester resins and phenol-formaldehyde
resins, [0112] plant-derived materials, such as wood, wood-plastic
composites, paper and paperboard, and [0113] animal-derived
materials such as leather.
[0114] It is particularly preferable that the phosphoric ester
preparations of the invention are used as flame retardants for
polyurethanes. It is very particularly preferable that the
phosphoric ester preparations are used as flame retardants for
polyurethane foams.
[0115] The polyurethane foams are flexible polyurethane foams or
rigid polyurethane foams. It is preferable that the phosphoric
ester preparations are used as flame retardants for flexible
polyurethane foams which are produced from polyether polyols, i.e.
flexible polyether-polyurethane foams. In an alternative, likewise
preferred, embodiment of the invention the phosphoric ester
preparations are used as flame retardants for flexible polyurethane
foams which are produced from polyester polyols, i.e. flexible
polyester-polyurethane foams.
[0116] The present invention further provides polyurethanes which
comprise at least one phosphoric ester preparation of the
invention. These polyurethanes can be produced in flame-retardant
form via suitable selection of the quantity of phosphoric ester
preparations present.
[0117] The flame-retardant polyurethanes of the invention can be
produced by reacting organic polyisocyanates with compounds having
at least two hydrogen atoms reactive towards isocyanates with
conventional blowing agents, stabilizers, activators and/or other
conventional auxiliaries and additives in the presence of at least
one phosphoric ester preparation of the invention.
[0118] The quantity used of the phosphoric ester preparations of
the invention is from 0.5 to 30 parts by weight, preferably from 3
to 25 parts by weight, based on 100 parts by weight polyol
component.
[0119] The polyurethanes are isocyanate-based polymers which mainly
have urethane groups and/or isocyanurate groups and/or allophanate
groups and/or uretdione groups and/or urea groups and/or
carbodiimide groups. The production of isocyanate-based polymers is
known per se and is described by way of example in German
Offenlegungschrift 16 94 142, 16 94 215 and 17 20 768, and also in
Kunststoff-Handbuch [Plastics handbook] Volume VII, Polyurethane
[Polyurethanes], edited by G. Oertel, Carl-Hanser-Verlag Munich,
Vienna 1993.
[0120] The flame-retardant polyurethanes of the invention are
thermoset polyurethanes, polyurethane foams, polyurethane
elastomers, thermoplastic polyurethanes, polyurethane coatings and
polyurethane lacquers, polyurethane adhesives and polyurethane
binders or polyurethane fibres.
[0121] In one preferred embodiment of the invention, the
flame-retardant polyurethanes of the invention are flame-retardant
polyurethane foams.
[0122] Polyurethane foams are broadly divided into flexible and
rigid foams. Although flexible and rigid foams can in principle
have approximately the same envelope density and the same
composition, flexible polyurethane foams have only little
crosslinking and exhibit only low resistance to deformation under
pressure. In contrast to this, the structure of rigid polyurethane
foams is composed of highly crosslinked units and rigid
polyurethane foam exhibits very high resistance to deformation
under pressure. Typical rigid polyurethane foam has closed cells
and has low thermal conductivity. Primary factors influencing the
subsequent foam structure and foam properties during the production
of polyurethanes via reaction of polyols with isocyanates are the
structure and molar mass of the polyol, and the reactivity and
number (functionality) of hydroxy groups present in the polyol.
Further details concerning rigid and flexible foams, the starting
materials that can be used to produce these, and also processes for
producing the same, are found in Norbert Adam, Geza Avar, Herbert
Blankenheim, Wolfgang Friederichs, Manfred Giersig, Eckehard
Weigand, Michael Halfmann, Friedrich-Wilhelm Wittbecker,
Donald-Richard Larimer, Udo Maier, Sven Meyer-Ahrens, Karl-Ludwig
Noble and Hans-Georg Wussow: "Polyurethanes", Ullmann's
Encyclopedia of Industrial Chemistry Release 2005, Electronic
Release, 7th Edn., Chapter 7 ("Foams"), Wiley-VCH, Weinheim
2005.
[0123] Preferred envelope densities of the polyurethane foams of
the invention are from 10 to 150 kg/m.sup.3. They particularly
preferably have envelope densities of from 20 to 50 kg/m.sup.3.
[0124] Starting components used for the production of the
isocyanate-based foams are as follows:
[0125] 1) Aliphatic, cycloaliphatic, araliphatic, aromatic and
heterocyclic polyisocyanates (e.g. W. Siefken in Justus Liebigs
Annalen der Chemie, 562, pp. 75-136), for example those of the
formula Q(NCO).sub.n, in which n=from 2 to 4, preferably from 2 to
3, and Q is an aliphatic hydrocarbon moiety having from 2 to 18,
preferably from 6 to 10, C atoms, a cycloaliphatic hydrocarbon
moiety having from 4 to 15, preferably from 5 to 10, C atoms, an
aromatic hydrocarbon moiety having from 6 to 15, preferably from 6
to 13, C atoms or an araliphatic hydrocarbon moiety having from 8
to 15, preferably from 8 to 13, C atoms. Particular preference is
generally given to the polyisocyanates that derive from tolylene
2,4- and/or 2,6-diisocyanate or from diphenylmethane 4,4'- and/or
2,4'-diisocyanate, these being readily obtainable in industry.
[0126] 2) Compounds having at least two hydrogen atoms reactive
towards isocyanates with molar mass from 400 to 8000 g/mol ("polyol
component"). These are not only compounds having amino groups,
thiol groups or carboxy groups but also preferably compounds having
hydroxy groups, in particular compounds having from 2 to 8 hydroxy
groups. If the polyurethane foam is to he a flexible foam, it is
preferable to use polyols with molar masses from 2000 to 8000 g/mol
and from 2 to 6 hydroxy groups per molecule. If, in contrast, the
intention is to produce a rigid foam it is preferable to use highly
branched polyols with molar masses from 400 to 1000 g/mol and from
2 to 8 hydroxy groups per molecule. The polyols are polyethers and
polyesters, and also polycarbonates and polyesteramides, these
being known per se for the production of homogeneous and of
cellular polyurethanes, being described for example in German
Offenlegungschrift 28 32 253. Preference is given in the invention
to the polyesters and polyethers having at least two hydroxy
groups.
[0127] The polyurethane foams of the invention can therefore be
produced in the form of rigid or flexible foams via appropriate
selection, easily found in the prior art, of the starting
materials.
[0128] Other optional starting components are compounds having at
least two hydrogen atoms reactive towards isocyanates and molar
mass from 32 to 399 g/mol. Again here these are compounds having
hydroxy groups and/or amino groups and/or thiol groups and/or
carboxy groups, preferably compounds having hydroxy groups and/or
amino groups, where said compounds serve as chain extenders or
crosslinking agents. These compounds generally have from 2 to 8,
preferably from 2 to 4 hydrogen atoms reactive towards isocyanates.
Examples of these are likewise described in German
Offenlegungschrift 28 32 253.
[0129] 3) Water and/or volatile organic substances as blowing
agent, e.g. n-pentane, isopentane, cyclopentane, acetone,
halogenated alkanes, such as trichloromethane, methylene chloride
or chlorofluoroalkanes, CO.sub.2 and others.
[0130] 4) Concomitant use is optionally made of auxiliaries and
additions such as catalysts of the type known per se,
surface-active additives such as emulsifiers and foam stabilizers,
reaction retarders, e.g. acidic substances such as hydrochloric
acid or organic acyl halides, and also cell regulators of the type
known per se, for example paraffins or fatty alcohols and
dimethylpolysiloxanes, and also pigments or dyes and other flame
retardants, stabilizers to counter effects of ageing and of
weathering, core-discoloration inhibitors, plasticizers and
fungistatic and bacteriostatic substances, and also fillers such as
barium sulphate, kieselguhr, carbon black or purified chalk (German
Offenlegungschrift 27 32 292). Particular core-discoloration
inhibitors that can be present are sterically hindered
trialkylphenols, alkyl esters of
3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid,
benzofuran-2-ones, secondary aromatic amines, phosphites,
phenothiazines or tocopherols.
[0131] The following compounds can also be present as further flame
retardants alongside the phosphoric ester preparations of the
invention in the polyurethanes of the invention: [0132] organic
phosphorus compounds such as triethyl phosphate, triphenyl
phosphate, diphenyl cresyl phosphate, tricresyl phosphate,
isopropylated or butylated aryl phosphates, aromatic bisphosphates,
neopentyl glycol bis(diphenyl phosphate), chlorinated phosphoric
esters such as tris(chloroisopropyl)phosphate or
tris(dichloropropyl)phosphate, dimethyl methanephosphonate, diethyl
ethanephosphonate, dimethyl propanephosphonate, diethylphosphinic
acid derivatives and salts of diethylphosphinic acid, other
oligomeric phosphates or phosphonates, hydroxylated phosphorus
compounds, 5,5-dimethyl-1,3,2-dioxaphosphorinane 2-oxide
derivatives, 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide
(DOPO) and its derivatives, [0133] inorganic phosphorus compounds
such as ammonium phosphate, ammonium polyphosphate, melamine
phosphate, melamine polyphosphate, [0134] nitrogen compounds such
as melamine, melamine cyanurate, [0135] bromine compounds such as
alkyl esters of a tetrabromobenzoic acid, brominated dials produced
from tetrabromophthalic anhydride, brominated polyols, brominated
diphenyl ethers, [0136] inorganic flame retardants such as
aluminium hydroxide, boehmite, magnesium hydroxide, expanded
graphite or clay minerals.
[0137] Other examples of surface-active additives and foam
stabilizers that can optionally be used concomitantly in the
invention, and also of cell regulators, reaction retarders,
stabilizers, flame-retardant substances, plasticizers, colorants
and fillers, and also fungistatic and bacteriostatic substances are
described in Kunststoff-Handbuch [Plastics Handbook], Volume VII,
Carl-Hanser-Verlag, Munich, 1993, pp. 104 to 123, as also are
details concerning the mode of use and of action of these
additives,
[0138] The present invention further provides a process for the
production of polyurethanes via reaction of organic polyisocyanates
with compounds having at least two hydrogen atoms reactive towards
isocyanates and conventional blowing agents, stabilizers,
catalysts, activators and/or other conventional auxiliaries and
additives at from 20 to 80.degree. C., by using a quantity of from
0.5 to 30 parts by weight, based on 100 parts by weight of polyol
component, of at least one phosphoric ester preparation of the
invention. It is preferable that the quantity used of the
phosphoric ester preparations is from 3 to 25 parts by weight,
based on 100 parts by weight of polyol component.
[0139] The process for the production of polyurethanes of the
invention is carried out by reacting the reaction components
described above in the single-stage process known per se, in the
prepolymer process or in the semiprepolymer process, often with use
of machinery such as that described in U.S. Pat. No. 2,764,565.
Details concerning processing equipment which can also be used in
the invention are described in Kunststoff-Handbuch [Plastics
Handbook] Volume VII, Polyurethane [Polyurethanes], edited by G.
Oertel, Carl-Hanser-Verlag, Munich, Vienna 1993, pp. 139 to
192.
[0140] The process of the invention can also produce cold-curing
foams (GB Patent 11 62 517, German Offenlegungschrift 21 53 086).
However, it is also of course possible to produce foams via block
foaming or by the twin-belt process known per se. Polyisocyanurate
foams are produced by using the processes and conditions known for
that purpose.
[0141] The process of the invention permits the production of
polyurethane foams in the form of rigid or flexible foams
continuously or batchwise, or in the form of foam mouldings.
Preference is given to the process of the invention in the
production of flexible foams produced via a block foaming
process.
[0142] The polyurethanes obtainable in the invention are preferably
used in furniture cushioning, textile inlays, mattresses, vehicle
seats, armrests, components, seat cladding and dashboard cladding,
cable sheathing, gaskets, coatings, lacquers, adhesives, adhesion
promoters and fibres.
[0143] The present invention provides the use of the phosphoric
ester preparations of the invention as hydraulic fluids or for the
production of hydraulic fluids. It is preferable that the
phosphoric ester preparations are used in flame-retardant hydraulic
fluids.
[0144] The phosphoric ester preparations of the invention can be
produced from known components by known methods. The liquid
phosphoric ester preparations are easy to meter and are therefore
very easy to process. By virtue of the reduced hygroscopicity,
there is reduced risk of undesired contamination with water.
[0145] The examples below provide further explanation of the
invention, but there is no intention that the invention be
restricted thereby.
EXAMPLES
Production Example
[0146] Oligomer mixture a) of poly(alkylene phosphates) of the
formula (I) where R.sup.1.dbd.R.sup.2.dbd.R.sup.3.dbd.R.sup.4=ethyl
and A=--CH.sub.2CH.sub.2OCH.sub.2CH.sub.2--
[0147] 306.7 parts by weight of phosphorus oxychloride were charged
to a reactor with stirrer, dropping funnel, reflux condenser and
vacuum equipment. The temperature of the phosphorus oxychloride was
controlled to from 10 to 20.degree. C. A vacuum of from 500 to 700
mbar was applied and 118.7 parts by weight of diethylene glycol
were added dropwise. Once the dropwise addition had ended, the
pressure was lowered further to a final value of from 5 to 15 mbar
and the temperature was raised to from 20 to 30.degree. C. The
residue was an almost colourless liquid.
[0148] 618.2 parts by weight of ethanol were used as initial charge
at from 20 to 30.degree. C. in another reactor with stirrer,
dropping funnel and reflux condenser, and the residue obtained
above was admixed. Stirring of the mixture was continued at from 20
to 30.degree. C. until the reaction ended, and the mixture was then
neutralized via addition of concentrated aqueous sodium hydroxide
solution. A sufficient amount of dichloromethane and water was then
added to give two clear liquid phases. These were separated, and
the organic phase was freed from the dichloromethane, excess
ethanol and water via distillation. The residue was the oligomer
mixture of the invention in the form of a colourless liquid. The
viscosity of the product was determined at 23.degree. C. by a
commercially available falling-ball viscometer, and was 58
[mPas].
[0149] Determination of the Average Value of the Number of
Repeating Units F in the Molecules Corresponding to the Formula (I)
Present in the Oligomer Mixture A) in Accordance with Above
Production Specification
[0150] Analysis via gel permeation chromatography (GPC) showed that
the product produced according to the above specification was an
oligomer mixture. The number-average molar mass M.sub.n of the
oligomer mixture was determined via GPC with tetrahydrofuran as
eluent against polystyrene standards by a method based on that of
DIN 55672-1:2007-08. The average value of the number of repeating
units n in the poly(alkylene phosphates) corresponding to the
formula (I) present in the oligomer mixture was calculated in
accordance with the following formula from the number-average molar
mass M.sub.n measured:
n=(M.sub.n-M.sub.E)/M.sub.R [0151] where [0152] n: is the average
value of the number of repeating units of the poly(alkylene
phosphates) of the formula (I) present in the oligomer mixture,
[0153] M.sub.n: is the number-average molar mass in g/mol
determined via gel permeation chromatography, [0154] M.sub.E: is
the sum of the molar masses of the terminal groups in g/mol and
[0155] M.sub.R: is molar mass of the repeating unit in g/mol.
[0156] For the oligomer mixtures of poly(alkylene phosphates) of
the formula (I) produced, where
R.sup.1.dbd.R.sup.2.dbd.R.sup.3.dbd.R.sup.4=ethyl and
A=--CH.sub.2CH.sub.2OCH.sub.2CH.sub.2--, the values are
M.sub.E=182.16 g/mol and M.sub.R=194.14 g/mol. The value obtained
for M.sub.n was 462 and thus n=1.44.
[0157] Determination of Water Absorption
[0158] The oligomer mixture a) produced in accordance with the
above specification was used for the Examples. Water absorption was
determined on the pure oligomer mixture a) (Comparative Example
M-CE1), and also on mixtures of 50% by weight of oligomer mixture
a) and 50% by weight of phosphoric ester b) according to Table 1.
All of the phosphoric esters listed in Table 1 were commercially
obtainable products with acid number <0.1 mg KOH/g. For
determination of water absorption, 100 ml of each mixture to be
tested were charged to a 250 ml glass beaker (height 12 cm,
diameter 6 cm) and placed, uncovered, for 7 days in a chamber under
controlled climatic conditions at 23.degree. C. and 50% relative
humidity. The water content of the mixtures was determined by means
of Karl-Fischer titration in accordance with DIN 51777. Each of the
samples was homogenized by stirring before the water
determination.
TABLE-US-00001 TABLE 1 Phosphoric esters b) used and water
solubility of these Solubility in water Common name Chemical name
at 25.degree. C. [g/l] TEP Triethyl phosphate miscible TiBP
Triisobutyl phosphate 0.27 TDCP Tris(2,3-dichloroisopropyl) 0.10
phosphate DPC Diphenyl cresyl phosphate 0.0026 RDP Resorcinol
bis(diphenyl 0.0011 phosphate) TCPP Tris (2-chloroisopropyl) 1.08
phosphate TBPP tert-Butylated triphenyl 0.0027 phosphate TBEP
Tris(2-butoxyethyl) 0.70 phosphate IPP Isopropylated triphenyl
0.00033 phosphate
TABLE-US-00002 TABLE 2 Water absorption after 7 days for phosphoric
ester mixtures of the invention made of 50% by weight of oligomer
mixture a) and 50% by weight of phosphoric ester b) (Examples M-IE1
to M-IE8) and Comparative Examples M-CE1 to M-CE2 not of the
invention Water absorption after 7 days Mixture Neutral phosphoric
ester [% by weight] M-CE1 -- 2.30 M-CE2 TEP 3.09 M-IE1 TiBP 1.91
M-IE2 DPC 0.91 M-IE3 IPP 0.70 M-IE4 TBPP 0.87 M-IE5 RDP 0.90 M-IE6
TCPP 1.24 M-IE7 TDCP 0.87 M-IE8 TBEP 2.05
[0159] Evaluation of Water Absorption Results
[0160] According to the results listed in Table 2, the oligomer
mixture a) alone (Comparative Example M-CE1) exhibits considerable
water absorption under the test conditions. In the absence of
complicated precautions, the product rapidly absorbs a quantity of
water that can be problematic in industrial applications.
[0161] The phosphoric ester preparations M-IE1 to M-IE8 of the
invention exhibit markedly lower water absorption than the oligomer
mixture a) alone. They therefore feature reduced hygroscopicity,
and this is an advantage in water-sensitive industrial
applications.
[0162] In contrast, the mixture M-CE2, not of the invention, made
of the oligomer mixture a) and of the phosphoric ester triethyl
phosphate with water solubility of more than 3.0 g/l at 25.degree.
C. absorbs markedly more water than the oligomer mixture a) alone,
and therefore has markedly poorer suitability for water-sensitive
industrial applications.
[0163] Production of Flexible Polyurethane Foams
TABLE-US-00003 TABLE 3 Raw materials used for the production of
flexible polyether-polyurethane foams Component Function
Description A Polyol Arcol .RTM. 1105 (Bayer MaterialScience),
polyether polyol with OHN 56 mg KOH/g B Blowing agent Water C
Catalyst Addocat 108 .RTM. (Rhein Chemie), 70% solution of
bis(2-dimethylaminoethyl) ether in dipropylene glycol D Catalyst
Addocat .RTM. SO (Rhein Chermie), tin(II) 2-ethylhexanoate E
Stabilizer Tegostab .RTM. B 8232 (Degussa), silicone stabilizer M
Flame retardant Phosphoric ester preparations from Table 2 G
Diisocyanate Desmodur .RTM. T 80 (Bayer MaterialScience), tolylene
diisocyanate, isomer mixture
[0164] Production of Flexible Polyether-Polyurethane Foams
[0165] Table 3 states the raw materials for the production of
flexible polyether-polyurethane foams. The components stated in
terms of type and quantity in Table 4, with the exception of the
diisocyanate (component G), were mixed to give a homogeneous
mixture. The diisocyanate was then added and incorporated by brief
vigorous stirring. After a cream time of from 15 to 20 s and a full
rise time of from 170 to 200 s, a flexible polyether-polyurethane
foam was obtained with envelope density 33 kg/m.sup.3. Uniformly
fine-pored foams were obtained in all of the Examples.
[0166] Determination of Flame Retardancy
[0167] The flexible polyurethane foams (polyether and polyester)
were tested in accordance with the specifications of the Federal
Motor Vehicle Safety Standards FMVSS 302 and allocated to the fire
classes SE (self-extinguishing), SE/NBR (self-extinguishing/no
burning rate), SE/BR (self-extinguishing/with burning rate), BR
(burning rate) and RB (rapid-burning). The fire tests were carried
out five times for each Example. The worst result from each series
of five has been reported in Table 4.
TABLE-US-00004 TABLE 4 Composition (parts by weight) and test
results for Examples IE1 to IE2 of the invention and for
Comparative Examples CE0 to CE1, not of the invention, relating to
flexible polyether-polyurethane foams Example CE0 CE1 IE1 IE2 A 100
100 100 100 B 3.0 3.0 3.0 3.0 C 0.08 0.08 0.08 0.08 D 0.16 0.16
0.16 0.16 E 0.80 0.80 0.80 0.80 M-CE1 6 M-IE4 6 M-IE5 6 G 40.9 40.9
40.9 40.9 MVSS class RB SE SE SE
[0168] Evaluation of Results Relating to Flexible
Polyether-Polyurethane Foams
[0169] In the absence of a flame retardant (Comparative Example
CEO) the flexible polyurethane foam is rapidly consumed by
combustion (MVSS fire class RB). Foams with an oligomer mixture a)
alone (Comparative Example CEO, and also with the phosphoric ester
preparations of the invention (Inventive Examples IE1 and IE2)
achieve the best MVSS fire class SE (self-extinguishing) when six
parts of flame retardant are used.
[0170] Examples IE1 and IE2 show that the phosphoric ester
preparations of the invention with reduced hygroscopicity exhibit
the same flame-retardant effect as the known hygroscopic oligomer
mixtures a) alone.
[0171] Production of Flexible Polyester-Polyurethane Foams
[0172] Table 5 states the raw materials for the production of
flexible polyester-polyurethane foams. The components stated in
terms of type and quantity in Table 6, with the exception of the
two diisocyanates (components G and H), were mixed to give a
homogeneous mixture. The two premixed diisocyanates were then added
and incorporated by brief vigorous stirring. After a cream time of
from 10 to 15 s and a full rise time of from 70 to 80 s, a flexible
polyester-polyurethane foam was obtained with envelope density 29
kg/m.sup.3. The foam structure of the flexible
polyester-polyurethane foams was dependent on the flame retardants
used. It is recorded in Table 6 as "uniformly fine-pored" ("uf") or
"non-uniformly coarse-pored" ("nc").
TABLE-US-00005 TABLE 5 Raw materials used for the production of
flexible polyester-polyurethane foams (Inventive Examples IE6 and
IE7 and Comparative Examples CE2 to CE4, not of the invention)
Component Function Description A Polyol Desmophen .RTM. 2200 B
(Bayer MaterialScience), polyester polyol with OHN 60 mg KOH/g B
Blowing agent Water C Catalyst Niax .RTM. A-30 (Momentive), amine D
Catalyst Addocat .RTM. 117 (Rhein Chemie), tertiary amine E
Stabilizer Tegostab .RTM. B 8324 (Degussa), silicone stabilizer
M-IE4 and Flame retardant Phosphoric ester preparations from Table
2 M-IE5 M-CE3 Flame retardant Mixture of 50% by weight of Fyrol
.RTM. PNX from ICL-IP (oligomeric phosphate esters of the formula
EtO--[P(.dbd.O)OEt--
CH.sub.2CH.sub.2--].sub.n--P(.dbd.O)(OEt).sub.2, CAS Reg. No.
184538-58-7, M.sub.n = 640 g/mol from GCP (see above), average
value of the number of repeating units n = 3.01; viscosity 1241
mPas at 23.degree. C.) with 50% by weight of RDP G Diisocyanate
Desmodur .RTM. T 80 (Bayer MaterialScience), tolylene diisocyanate,
isomer mixture H Diisocyanate Desmodur .RTM. T 65 (Bayer
MaterialScience), tolylene diisocyanate, isomer mixture
TABLE-US-00006 TABLE 6 Composition (parts by weight) and test
results for Examples IE3 to IE4 of the invention and for
Comparative Examples CE2 to CE4, not of the invention, relating to
flexible polyester-polyurethane foams Example CE2 CE3 CE4 IE3 IE4 A
100 100 100 100 100 B 4.0 4.0 4.0 4.0 4.0 C 0.25 0.25 0.25 0.25
0.25 D 0.25 0.25 0.25 0.25 0.25 E 1.0 1.0 1.0 1.0 1.0 M-CE1 6 M-CE3
6 M-IE4 6 M-IE5 6 G 24.1 24.1 24.1 24.1 24.1 H 24.1 24.1 24.1 24.1
24.1 Foam structure uf uf nc uf uf MVSS class RB SE -- SE SE
[0173] Evaluation of the Results Relating to Flexible
Polyester-Polyurethane Foams
[0174] In the absence of a flame retardant (Comparative Example
CE2) the flexible polyester-polyurethane foam features a uniformly
fine-pored foam structure, but is rapidly consumed by combustion
(MVSS fire class RB). Addition of 6 parts of an oligomer mixture a)
alone in accordance with the production specification stated above
(Comparative Example CE3) does not alter the foam structure and
permits achievement of the best MVSS fire class SE
(self-extinguishing). However, the high hygroscopicity of the pure
oligomer mixture a) M-CE1 is disadvantageous.
[0175] A mixture described in WO 2001/018088 A1, made of an
oligomer mixture of poly(alkylene phosphate) of the formula
EtO-[P(.dbd.O)OEt-CH.sub.2CH.sub.2--].sub.n--P(.dbd.O)(OEt).sub.2
(M-CE3; CAS Reg. No. 184538-58-7, average value of the number of
repeating units n=3.01) and RDP in a ratio by mass of 1:1 cannot be
successfully processed to give a flexible polyester-polyurethane
foam (Comparative Example CE4). The foam is non-uniformly
coarse-pored and thus unusable. This shows that the mixture M-CE3
from the prior art is not compatible with polyester polyols.
[0176] In contrast to this, the phosphoric ester preparations of
the invention (Inventive Examples IE3 and IE4) permit the
production of foams with the desired, uniformly fine-pored foam
structure. Inventive Example IE4 uses the phosphoric ester
preparation M-IE5 of the invention which, like M-CE3, comprises 50%
by weight of RDP as phosphoric ester b), and is therefore directly
comparable with Comparative Example CE4. The foams from Inventive
Examples IE3 and IE4 achieve the best MVSS fire class SE
(self-extinguishing) with 6 parts of flame retardant.
[0177] Examples IE3 and IE4 show that the phosphoric ester
preparations of the invention with reduced hygroscopicity have good
processability with polyester polyols and exhibit the same
flame-retardant effect as the known hygroscopic oligomer mixtures
a) alone.
* * * * *