U.S. patent application number 16/306192 was filed with the patent office on 2021-04-29 for method for the improved oxidation of secondary amine groups.
This patent application is currently assigned to Evonik Operations GmbH. The applicant listed for this patent is Evonik Operations GmbH. Invention is credited to Michael FLITTNER, Michael KORELL, Christine KORNER, Christian MEIER, Jorn Klaus Erich WOLF.
Application Number | 20210122864 16/306192 |
Document ID | / |
Family ID | 1000005331274 |
Filed Date | 2021-04-29 |
![](/patent/app/20210122864/US20210122864A1-20210429\US20210122864A1-2021042)
United States Patent
Application |
20210122864 |
Kind Code |
A1 |
MEIER; Christian ; et
al. |
April 29, 2021 |
METHOD FOR THE IMPROVED OXIDATION OF SECONDARY AMINE GROUPS
Abstract
The present invention relates to a process for oxidizing
secondary amino groups to the corresponding radical nitroxyl groups
within a polymer comprising, for example,
2,2,6,6-tetramethylpiperidinyl units. The process assures a
particularly high degree of oxidation.
Inventors: |
MEIER; Christian;
(Darmstadt, DE) ; FLITTNER; Michael; (Mombris,
DE) ; KORNER; Christine; (Aschaffenburg, DE) ;
KORELL; Michael; (Bochum, DE) ; WOLF; Jorn Klaus
Erich; (Essen, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Evonik Operations GmbH |
Essen |
|
DE |
|
|
Assignee: |
Evonik Operations GmbH
Essen
DE
|
Family ID: |
1000005331274 |
Appl. No.: |
16/306192 |
Filed: |
August 31, 2017 |
PCT Filed: |
August 31, 2017 |
PCT NO: |
PCT/EP2017/071876 |
371 Date: |
November 30, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01M 10/0525 20130101;
H01M 4/604 20130101; C08F 2810/00 20130101; C08F 220/34 20130101;
C08F 2800/20 20130101 |
International
Class: |
C08F 220/34 20060101
C08F220/34; H01M 4/60 20060101 H01M004/60; H01M 10/0525 20060101
H01M010/0525 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 6, 2016 |
EP |
16187383.1 |
Claims
1: A process for preparing a polymer P.sup.1 comprising n.sup.1
repeat units of a chemical structure (I) ##STR00014## said process
comprising: oxidizing a polymer P.sup.2 comprising n.sup.2 repeat
units of a chemical structure (II) ##STR00015## in a solvent
comprising water and ethanol, wherein the ethanol is present in the
solvent in deficiency relative to water, wherein n.sup.1, n.sup.2
are each independently an integer in a range of 4-3 000 000,
wherein the repeat units of the chemical structure (I) within the
polymer P.sup.1 are the same or at least partly different from one
another, wherein the repeat units of the chemical structure (I)
within the polymer P.sup.1 are joined to one another in such a way
that the bond identified by "#" in a particular repeat unit is
joined to the bond identified by "##" in an adjacent repeat unit,
wherein the repeat units of the chemical structure (II) within the
polymer P.sup.2 are the same or at least partly different from one
another, wherein the repeat units of the chemical structure (II)
within the polymer P.sup.2 are joined to one another in such a way
that the bond identified by "#" in a particular repeat unit is
joined to the bond identified by "##" in an adjacent repeat unit,
and wherein, in the chemical structures (I) and (II), the R.sup.1,
R.sup.2, R.sup.3, R.sup.4, R.sup.5 radicals are each independently
selected from the group consisting of hydrogen, branched alkyl
group having 1 to 4 carbon atoms and unbranched alkyl group having
1 to 4 carbon atoms, X is selected from the group consisting of
*--CH.sub.2--C'H--CH.sub.2--**, *--C'H--CH.sub.2--**, and
*--C'.dbd.CH--**, wherein "*" in each case denotes the bond to the
carbon atom joined to R.sup.1 and R.sup.2, "**" in each case
denotes the bond to the carbon atom joined to R.sup.3 and R.sup.4,
"C" denotes a carbon atom additionally joined to the Y radical, Y
is selected from the bridging radicals (III) and (IV), wherein
(III) has a structure
&-(Y.sup.1).sub.p1--[C.dbd.X.sup.1].sub.p2--(Y.sup.2).sub.p3--B--(Y.sup.3-
).sub.p6--[C.dbd.X.sup.2].sub.p5--(Y.sup.4).sub.p4--&&, and
wherein (IV) has a structure
&-(Y.sup.5).sub.p9--(C.dbd.X.sup.3).sub.p8--(Y.sup.6).sub.p7-&&,
wherein, in the bridging radicals (III) and (IV), p1, p2, p3 are
each 0 or 1, with the proviso that it is not simultaneously the
case that p1=p3=1 and p2=0, p4, p5, p6 are each 0 or 1, with the
proviso that it is not simultaneously the case that p1=p6=1 and
p5=0, p7, p8, p9 are each 0 or 1, with the proviso that it is not
simultaneously the case that p7=p9=1 and p8=0, and that, when p7=1
and p8=0, p9=0, X.sup.1, X.sup.2, X.sup.3 are independently
selected from the group consisting of O, and S, Y.sup.1, Y.sup.2,
Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6 are independently selected from
the group consisting of O, S, NH, and N-alkyl, and Y.sup.1, when
p1=1, p2=p3=0, may also be N O., Y.sup.4, when p4=1, p5=p6=0, may
also be N O., Y.sup.5, when p9=1, p7=p8=0, may also be N O., B is a
divalent, optionally substituted (hetero)aromatic radical or a
divalent, optionally substituted aliphatic radical, wherein the
optionally substituted aliphatic radical may additionally have at
least one group selected from the group consisting of ether,
thioether, optionally nitroxylated amino ether, carbonyl group,
carboxylic ester group, carboxamide group, sulphonic ester group,
and phosphoric ester, "&&" for Y denotes the bond via which
Y is joined to X "&" for Y denotes the bond via which Y is
joined to the carbon atom joined to R.
2: The process according to claim 1, wherein X.sup.1, X.sup.2,
X.sup.3, Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6 are
independently selected from the group consisting of O, and S,
wherein B is a divalent, optionally substituted (hetero)aromatic
radical or a divalent, optionally substituted aliphatic radical,
and wherein the optionally substituted aliphatic radical may
additionally have at least one group selected from the group
consisting of ether, thioether, carbonyl group, carboxylic ester
group, sulphonic ester group, and phosphoric ester.
3: The process according to claim 2, wherein
R.sup.1.dbd.R.sup.2.dbd.R.sup.3.dbd.R.sup.4=methyl and
R.sup.5=hydrogen or methyl, wherein B is a divalent
(hetero)aromatic radical or a divalent aliphatic radical optionally
substituted by a group selected from the group consisting of --F,
--Cl, --Br, and --I, wherein the optionally substituted aliphatic
radical may additionally have at least one group selected from the
group consisting of ether, and thioether.
4: The process according to claim 3, wherein
X.sup.1=X.sup.2=X.sup.3=Y.sup.1=Y.sup.2=Y.sup.3=Y.sup.4=Y.sup.5=Y.sup.6=O-
, phenylene or an alkylene radical optionally substituted by at
least one group selected from the group consisting of --F, --Cl,
--Br, and --I.
5: The process according to claim 1, wherein
X=*--CH.sub.2--C'H--CH.sub.2--**.
6: The process according to claim 5, wherein the chemical structure
(I) has the following structure (II)'''', and the chemical
structure (II) has the following structure (II)'''': ##STR00016##
wherein R.sup.5=methyl or hydrogen.
7: The process according to claim 1, which is conducted at a
temperature T.sub.1.ltoreq.40.degree. C.
8: The process according to claim 1, wherein a mass ratio of water
to ethanol in the solvent is in a range of 51:49 to 99:1.
9: The process according to claim 1, wherein a proportion of a sum
total of the weights of ethanol and water in the solvent is at
least 50% by weight, based on a total weight of the solvent.
10: The process according to claim 8, wherein a proportion by
weight of all C.sub.1-C.sub.4 alcohols other than ethanol in the
solvent is less than 50% by weight, based on the weight of the
ethanol encompassed by the solvent.
11: The process according to claim 1, wherein n.sup.1, n.sup.2 are
each independently an integer in a range of 4-1 000 000.
Description
[0001] The present invention relates to a process for oxidizing
secondary amino groups to the corresponding radical nitroxyl groups
within a polymer comprising, for example,
2,2,6,6-tetramethylpiperidinyl units. The process assures a
particularly high degree of oxidation.
BACKGROUND OF THE INVENTION
[0002] Organic batteries are electrochemical cells which use an
organic charge storage material as active electrode material for
storing electrical charge. These secondary batteries are notable
for their exceptional properties, such as fast chargeability, long
lifetime, low weight, high flexibility and ease of processibility.
Active electrode materials for charge storage which have been
described in the prior art are various polymeric structures, for
example polymeric compounds having organic nitroxyl radicals as
active units (for example in WO 2012/133202 A1, WO 2012/133204 A1,
WO 2012/120929 A1, WO 2012/153866 A1, WO 2012/153865 A1 JP
2012-221574 A, JP 2012-221575 A, JP 2012-219109 A, JP 2012-079639
A, WO 2012/029556 A1, WO 2012/153865 A1, JP 2011-252106 A, JP
2011-074317 A, JP 2011-165433 A, WO 2011034117 A1 WO 2010/140512
A1, WO 2010/104002 A1, JP 2010-238403 A, JP 2010-163551 A, JP
2010-114042 A, WO 2010/002002 A1, WO 2009/038125 A1, JP 2009-298873
A, WO 2004/077593 A1, WO 2009/145225 A1, JP 2009-238612 A, JP
2009-230951 A, JP 2009-205918 A, JP 2008-234909 A, JP 2008-218326
A, WO 2008/099557 A1, WO 2007/141913 A1, US 2002/0041995 A1, EP
1128453 A2; A. Vlad, J. Rolland, G. Hauffman, B. Ernould, J.-F.
Gohy, CherriSusChem 2015, 8, 1692-1696) or polymeric compounds
having organic phenoxyl radicals or galvinoxyl radicals as active
units (for example US 2002/0041995 A1, JP 2002-117852 A).
[0003] Particular emphasis should be given here to
poly(2,2,6,6-tetramethylpiperidinyloxylmethacrylate), the synthesis
of which is described by K. Nakahara, S. Iwasa, M. Satoh, Y.
Morioka, J. Iriyarna, M. Suguro, E. Hasegawa, Chem Phys Lett 2002,
359, 351-354 and J. Kim, G. Cheruvally, J. Choi, J. Ahn, S. Lee, S.
Choi, C. Song, Solid State Ionics 2007, 178, 1546-1551. Further
synthesis methods are described in the following publications; JP
2006-022177 A, WO 2015/032951 A1, EP 1 752 474 A1, EP 1 911 775 A1,
EP 2 042 523 A1. Moreover, Liang Wenzhong also describes, in
Polymer Degradation and Stability 1991, 31, 353-364, nitroxidation
to form this polymer, wherein the solvent used is ethanol in
excess.
[0004] Particular emphasis should be given to EP 1 911 775 A1,
which describes a process for polymerizing
2,2,6,6-tetramethylpiperidinyl methacrylate and subsequently
oxidizing the secondary amino groups within the
2,2,6,6-tetramethylpiperidinyl unit to give a radical
2,2,6,6-tetramethylpiperidinyloxyl group ("nitroxylation"
hereinafter). The nitroxylation level (or oxidation level) achieved
in this prior art document is high at 95.5%. There is nevertheless
still a need to achieve an even better degree of oxidation.
[0005] In addition, EP 1 911 775 A1 states in paragraph [0046] that
the process is applicable within a wide temperature range of 0 to
90.degree. C. Nevertheless, it is apparent from the example of EP 1
911 775 A1 described in paragraphs [0053], [0054] and [0055] that
the polymerization should best be conducted at high temperatures
such as 80.degree. C.
[0006] However, performance at such a high temperature is
economically disadvantageous. On the industrial scale in
particular, it is desirable to be able to conduct of this reaction
without having to expend additional energy for heating of the
reaction solution. In some cases, it is additionally also desirable
to be able to conduct the reaction with cooling below 0.degree. C.,
since the cooling allows better control over the occurrence of
significant exotherms.
[0007] The problem addressed by the present invention is therefore
that of providing a process which achieves maximum oxidation of the
secondary amino groups in a polymer comprising
2,2,6,6-tetramethylpiperidinyl groups or similar groups to radical
nitroxyl groups. The process should lead to better oxidation rates,
specifically also at room temperature and lower temperatures.
[0008] A process which solves the aforementioned problem has now
surprisingly been found.
DETAILED DESCRIPTION OF THE INVENTION
[0009] 1) The present invention accordingly relates to processes
for preparing a polymer P.sup.1 comprising n.sup.1 repeat units of
the general chemical structure (I)
##STR00001##
[0010] which is characterized in that a polymer P.sup.2 comprising
n.sup.2 repeat units of the general chemical structure (II)
##STR00002##
[0011] is oxidized in a solvent comprising water and ethanol, where
the ethanol is present in the solvent n deficiency relative to
water, especially at a temperature T.sub.1.ltoreq.40.degree.
C.,
[0012] where n.sup.1, n.sup.2 are each independently an integer in
the range of 4-3 000 000, especially 4-1 000 000, preferably 4-100
000, more preferably 4-10 000, even more preferably 4-5000,
[0013] where the repeat units of the chemical structure (I) within
the polymer P.sup.1 are the same or at least partly different from
one another,
[0014] where the repeat units of the chemical structure (I) within
the polymer P.sup.1 are joined to one another in such a way that
the bond identified by "#" in a particular repeat unit is joined to
the bond identified by "##" in the adjacent repeat unit,
[0015] where the repeat units of the chemical structure (II) within
the polymer P.sup.2 are the same or at least partly different from
one another,
[0016] where the repeat units of the chemical structure (II) within
the polymer P.sup.2 are joined to one another in such a way that
the bond identified by "#" in a particular repeat unit is joined to
the bond identified by "##" in the adjacent repeat unit,
[0017] and where, in the chemical structures (I) and (II), the
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 radicals are selected
from the group consisting of hydrogen, branched or unbranched alkyl
group having 1 to 4 carbon atoms, preferably R.sup.1, R.sup.2,
R.sup.3, R.sup.4=methyl and R.sup.5=hydrogen or methyl,
[0018] X is selected from the group consisting of
*--CH.sub.2--C'H--CH.sub.2--**, *--C'H--CH.sub.2--**,
*--C.dbd.CH--**,
[0019] where "*" in each case denotes the bond to the carbon atom
joined to R.sup.1 and R.sup.2,
[0020] where "w*" in each case denotes the bond to the carbon atom
joined to R.sup.3 and R.sup.4,
[0021] where "C'" denotes a carbon atom additionally joined to the
Y radical,
[0022] where Y is selected from the bridging radicals (III) and
(IV), [0023] where (III) has the structure &-(Y.sup.1).sub.p1
[C.dbd.X.sup.1].sub.p2--(Y.sup.2).sub.p3--B--(Y.sup.3).sub.p6--[C.dbd.X.s-
up.2].sub.p5--(Y.sup.4).sub.p4--&&, [0024] and where (IV)
has the structure
&-(Y.sup.5).sub.p9--(C.dbd.X.sup.3).sub.p8--(Y.sup.6).sub.p7-&&-
, [0025] where, in the bridging radicals (III) and (IV), [0026] p1,
p2, p3 are each 0 or 1, with the proviso that it is not
simultaneously the case that p1=p3=1 and p2=0, [0027] p4, p5, p6
are each 0 or 1, with the proviso that it is not simultaneously the
case that p4=p6=1 and p5=0, [0028] p7, p8, p9 are each 0 or 1, with
the proviso that it is not simultaneously the case that p7=p9=1 and
p8=0, and that, when p7=1 and p8=0, p9=0, [0029] X.sup.1, X.sup.2,
X.sup.3 are independently selected from the group consisting of O,
S, [0030] Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6 are
independently selected from the group consisting of O, S, NH,
N-alkyl, [0031] and where Y.sup.1, when p1=1, p2=p3=0, may also be
N O., [0032] and where Y.sup.4, when p4=1, p5=p6=0, may also be N
O., [0033] and where Y.sup.5, when p9=1, p7=p8=0, may also be N O.,
[0034] B is a divalent, optionally substituted (hetero)aromatic
radical or a divalent, optionally substituted aliphatic radical,
where the optionally substituted aliphatic radical may additionally
have at least one group selected from ether, thioether, optionally
nitroxylated amino ether, carbonyl group, carboxylic ester group,
carboxamide group, sulphonic ester group, phosphoric ester,
[0035] and where "&&" for Y denotes the bond via which Y is
joined to X and where "&" for Y denotes the bond via which Y is
joined to the carbon atom joined to R.sup.5.
[0036] 2) In a particular embodiment of the present invention, the
invention relates to a process for preparing a polymer P.sup.1
comprising n.sup.1 repeat units of the general chemical structure
(I)
##STR00003##
[0037] which is characterized in that a polymer P.sup.2 comprising
n.sup.2 repeat units of the general chemical structure (II)
##STR00004##
[0038] is oxidized in a solvent comprising water and ethanol, where
the ethanol is present in the solvent in deficiency relative to
water, especially at a temperature T.sub.1.ltoreq.40.degree.
C.,
[0039] where n.sup.1, n.sup.2 are each independently an integer in
the range of 4-3 000 000, especially 4-1 000 000, preferably 4-100
000, more preferably 4-10 000, even more preferably 4-5000,
[0040] where the repeat units of the chemical structure (I) within
the polymer P.sup.1 are the same or at least partly different from
one another,
[0041] where the repeat units of the chemical structure (I) within
the polymer P.sup.1 are joined to one another in such a way that
the bond identified by "#" in a particular repeat unit is joined to
the bond identified by "##" in the adjacent repeat unit,
[0042] where the repeat units of the chemical structure (II) within
the polymer P.sup.2 are the same or at least partly different from
one another,
[0043] where the repeat units of the chemical structure (II) within
the polymer P.sup.2 are joined to one another in such a way that
the bond identified by "#" in a particular repeat unit is joined to
the bond identified by "##" in the adjacent repeat unit,
[0044] and where, in the chemical structures (I) and (II), the
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 radicals are selected
from the group consisting of hydrogen, branched or unbranched alkyl
group having 1 to 4 carbon atoms, preferably R.sup.1, R.sup.2,
R.sup.3, R.sup.4 methyl and R.sup.5 hydrogen or methyl,
[0045] X is selected from the group consisting of
*--CH.sub.2--C'H--CH.sub.2--**, *--C'H--CH.sub.2--**,
*--C.degree.=CH--**,
[0046] where "*" in each case denotes the bond to the carbon atom
joined to R.sup.1 and R.sup.2,
[0047] where "**" in each case denotes the bond to the carbon atom
joined to R.sup.3 and R.sup.4,
[0048] where "C'" denotes a carbon atom additionally joined to the
Y radical,
[0049] where Y is selected from the bridging radicals (III) and
(IV), [0050] where (III) has the structure
&-(Y.sup.1).sub.p1--[C.dbd.X.sup.1].sub.p2--(Y.sup.2).sub.p3--B--(Y.sup.3-
).sub.p6--[C.dbd.X.sup.2].sub.p5--(Y.sup.4).sub.p4--&&,
[0051] and where (IV) has the structure
&-(Y.sup.5).sub.p9--(C.dbd.X.sup.3).sub.p8--(Y.sup.6).sub.p7-&&,
[0052] where, in the bridging radicals (III) and (IV), [0053] p1,
p2, p3 are each 0 or 1, with the proviso that it is not
simultaneously the case that p1=p3=1 and p2=0, [0054] p4, p5, p6
are each 0 or 1, with the proviso that it is not simultaneously the
case that p4=p6=1 and p5=0, [0055] p7, p8, p9 are each 0 or 1, with
the proviso that it is not simultaneously the case that p7=p9=1 and
p8=0, and that, when p7=1 and p8=0, p9=0, [0056] X.sup.1, X.sup.2,
X.sup.3, r, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, are
independently selected from the group consisting of O, S, [0057] B
is a divalent, optionally substituted (hetero)aromatic radical or a
divalent, optionally substituted aliphatic radical, where the
optionally substituted aliphatic radical may additionally have at
least one group selected from ether, thioether, carbonyl group,
carboxylic ester group, sulphonic ester group, phosphoric
ester,
[0058] and where "&&" for Y denotes the bond via which Y is
joined to X and where "&" for Y denotes the bond via which Y is
joined to the carbon atom joined to R.sup.5.
[0059] 3) In a preferred embodiment of the present invention, the
invention relates to a process for preparing a polymer P.sup.1
comprising n.sup.1 repeat units of the general chemical structure
(I)
##STR00005##
[0060] which is characterized in that a polymer P.sup.2 comprising
n.sup.2 repeat units of the general chemical structure (II)
##STR00006##
[0061] is oxidized in a solvent comprising water and ethanol, where
the ethanol is present in the solvent in deficiency relative to
water, especially at a temperature T.sub.1.ltoreq.40.degree.
C.,
[0062] where n.sup.1, n.sup.2 are each independently an integer in
the range of 4-3 000 000, especially 4-1 000 000, preferably 4-100
000, more preferably 4-10 000, even more preferably 4-5000,
[0063] where the repeat units of the chemical structure (I) within
the polymer P.sup.1 are the same or at least partly different from
one another,
[0064] where the repeat units of the chemical structure (I) within
the polymer P.sup.1 are joined to one another in such a way that
the bond identified by "#" in a particular repeat unit is joined to
the bond identified by "##" in the adjacent repeat unit,
[0065] where the repeat units of the chemical structure (II) within
the polymer P.sup.2 are the same or at least partly different from
one another,
[0066] where the repeat units of the chemical structure (II) within
the polymer P.sup.2 are joined to one another in such a way that
the bond identified by "#" in a particular repeat unit is joined to
the bond identified by "##" in the adjacent repeat unit,
[0067] and where, in the chemical structures (I) and (II),
R.sup.1.dbd.R.sup.2=R.sup.3.dbd.R.sup.4=methyl and R.sup.5=hydrogen
or methyl,
[0068] X is selected from the group consisting of
*--O--CH.sub.2--C'H--CH.sub.2--**, *--C'H--CH.sub.2--**,
*--C'=CH--**,
[0069] where "*" in each case denotes the bond to the carbon atom
joined to R.sup.1 and R.sup.2,
[0070] where "**" in each case denotes the bond to the carbon atom
joined to R.sup.3 and R.sup.4,
[0071] where "C'" denotes a carbon atom additionally joined to the
Y radical,
[0072] where Y is selected from the bridging radicals (III) and
(IV), [0073] where (III) has the structure
&-(Y.sup.1).sub.p1--[C.dbd.X.sup.1].sub.p2--(Y.sup.2).sub.p3--B--(Y.sup.3-
).sub.p6--[C.dbd.X.sup.2].sub.p5--(Y.sup.4).sub.p4.&&,
[0074] and where (IV) has the structure
ae(Y.sup.5).sub.p9--(C.dbd.X.sup.3).sub.p8--(Y.sup.5).sub.p7-&&,
[0075] where, in the bridging radicals (III) and (IV), [0076] p1,
p2, p3 are each 0 or 1, with the proviso that it is not
simultaneously the case that p1=p3=1 and p2=0, [0077] p4, p5, p6
are each 0 or 1, with the proviso that it is not simultaneously the
case that p4=p6=1 and p5=0, [0078] p7, p8, p9 are each 0 or 1, with
the proviso that it is not simultaneously the case that p7=p9=1 and
p8=0, and that, when p7=1 and p8=0, p9=0, [0079] X.sup.1, X.sup.2,
X.sup.3, Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6 are
independently selected from the group consisting of O, S, [0080] B
is a divalent (hetero)aromatic radical, preferably phenylene, or a
divalent aliphatic radical optionally substituted by at least one
group selected from --F, --Cl, --Br, --I, where the optionally
substituted aliphatic radical may additionally have at least one
group selected from ether, thioether,
[0081] and where "&&," for Y denotes the bond via which Y
is joined to X and where "&" for Y denotes the bond via which Y
is joined to the carbon atom joined to R.sup.5.
[0082] 4) In a more preferred embodiment of the present invention,
the invention relates to a process for preparing a polymer P.sup.1
comprising n.sup.1 repeat units of the general chemical structure
(I)
##STR00007##
[0083] which is characterized in that a polymer P.sup.2 comprising
n.sup.2 repeat units of the general chemical structure (II)
##STR00008##
[0084] is oxidized in a solvent comprising water and ethanol, where
the ethanol is present in the solvent in deficiency relative to
water, especially at a temperature T.sub.1.ltoreq.40.degree.
C.,
[0085] where n.sup.1, n.sup.2 are each independently an integer in
the range of 4-3 000 000, especially 4-1 000 000, preferably 4-100
000, more preferably 4-10 000, even more preferably 4-5000,
[0086] where the repeat units of the chemical structure (I) within
the polymer P.sup.1 are the same or at least partly different from
one another,
[0087] where the repeat units of the chemical structure (I) within
the polymer P.sup.1 are joined to one another in such a way that
the bond identified by "#" in a particular repeat unit is joined to
the bond identified by "##" in the adjacent repeat unit,
[0088] where the repeat units of the chemical structure (II) within
the polymer P.sup.2 are the same or at least partly different from
one another,
[0089] where the repeat units of the chemical structure (II) within
the polymer P.sup.2 are joined to one another in such a way that
the bond identified by "#" in a particular repeat unit is joined to
the bond identified by "##" in the adjacent repeat unit,
[0090] and where, in the chemical structures (I) and (II),
R.sup.1.dbd.R.sup.2=R.sup.2.dbd.R.sup.4=methyl and R.sup.5=hydrogen
or methyl,
[0091] X is selected from the group consisting of
*--CH.sub.2--C'H--CH.sub.2--**, *--C'H--CH.sub.2--**,
*--C.degree.=CH--**,
[0092] where "*" in each case denotes the bond to the carbon atom
joined to R.sup.1 and R.sup.2,
[0093] where "**" in each case denotes the bond to the carbon atom
joined to R.sup.3 and R.sup.4,
[0094] where "C'" denotes a carbon atom additionally joined to the
Y radical,
[0095] where Y is selected from the bridging radicals (ID) and
(IV), [0096] where (III) has the structure
&-(Y.sup.1).sub.p1--[C.dbd.X.sup.1].sub.p2--(Y.sup.2).sub.p3--B--(Y.sup.3-
).sub.p6[C.dbd.X.sup.2].sub.p5--(Y.sup.4).sub.p4--&&,
[0097] and where (IV) has the structure
&-(Y.sup.5).sub.p9--(C.dbd.X.sup.3).sub.p8--(Y.sup.5).sub.p7-&&,
[0098] where, in the bridging radicals (III) and (IV), [0099] p1,
p2, p3 are each 0 or 1, with the proviso that it is not
simultaneously the case that p1=p3=1 and p2=0, [0100] p4, p5, p6
are each 0 or 1, with the proviso that it is not simultaneously the
case that p4=p6=1 and p5=0, [0101] p7, p8, p9 are each 0 or 1, with
the proviso that it is not simultaneously the case that p7=p9=1 and
p8=0, and that, when p7=1 and p8=0, p9=0, [0102]
X.sup.1=X.sup.2=X.sup.3=Y.sup.1=Y.sup.2=Y.sup.3=Y.sup.4=Y.sup.5=Y.-
sup.5=O, [0103] B is phenylene, or an alkylene radical which is
optionally substituted by at least one group selected from --F,
--Cl, --Br, --I and is preferably unsubstituted and preferably
comprises 1 to 10 carbon atoms,
[0104] and where "&&" for Y denotes the bond via which Y is
joined to X and where "&" for Y denotes the bond via which Y is
joined to the carbon atom joined to R.sup.5.
[0105] In the embodiments described in points 1) to 4), X is
selected from the group consisting of
*--CH.sub.2--C'H--CH.sub.2--**, *--C'H--CH.sub.2--**,
*--C'.dbd.CH--**.
[0106] When X=*--CH.sub.2--C'H--CH.sub.2--**, the general chemical
structure (I) has the following structure of, and the general
chemical structure (II) has the following structure (II)':
##STR00009##
[0107] where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, Y have
the definitions described in the respective embodiments.
[0108] When X=*--C'H--CH.sub.2--**, the general chemical structure
(I) has the following structure (I)'', and the general chemical
structure (II) has the following structure (III)'':
##STR00010##
[0109] where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, Y have
the definitions described in the respective embodiments.
[0110] When X=*--'.dbd.CH.sub.2--**, the general chemical structure
(I) has the following structure (II)''', and the general chemical
structure (II) has the following structure (II)''':
##STR00011##
[0111] where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, Y have
the definitions described in the respective embodiments.
[0112] It is particularly preferable here in accordance with the
invention and especially in the embodiments cited in points 1) to
4) when X=*--CH.sub.2--C'H--CH.sub.2--**.
[0113] Most preferably, in the process according to the invention,
the general chemical structure (I) has the following structure
(I)'''', and the general chemical structure (II) has the following
structure (II)'''':
##STR00012##
[0114] where R.sup.5=methyl or hydrogen, preferably
R.sup.5=methyl.
[0115] It will be apparent that the bridging radical (IV), when
p7=p8=p9=0, may also be a direct bond.
[0116] It is a particular feature of the process according to the
invention that it is performed at a temperature
T.sub.1.ltoreq.40.degree. C., preferably -25.degree.
C..ltoreq.T.sub.1.ltoreq.40.degree. C., more preferably -20.degree.
C..ltoreq.T.sub.1.ltoreq.40.degree. C., even more preferably
-12.degree. C..ltoreq.T.sub.1.ltoreq.30.degree. C., even more
preferably still 0.degree. C..ltoreq.T.sub.1.ltoreq.25.degree.
C.
[0117] "Where the ethanol is present in the solvent in deficiency
relative to water" means especially that the mass ratio of water to
ethanol in the solvent is in the range of 51:49 to 99:1, preferably
in the range of 1.1:1 to 98:2, more preferably in the range of
55:45 to 95:5, even more preferably in the range of 1.3:1 to 9:1,
even more preferably still in the range of 4:1 to 8.5:1, most
preferably in the range of 7.1:1 to 8.2:1.
[0118] It is further preferable that the proportion of the sum
total of the weights of ethanol and water in the solvent is at
least 50% by weight, more preferably at least 60% by weight, even
more preferably at least 70% by weight, even more preferably at
least 80% by weight, yet more preferably at least 90% by weight,
even more preferably still at least 95% by weight, most preferably
at least 99% by weight, based on the total weight of the
solvent.
[0119] The solvent may, as well as water and ethanol, include
further constituents, especially selected from the group consisting
of halogenated hydrocarbons, aliphatic nitriles, aromatic nitriles,
alcohols other than ethanol, aromatic hydrocarbons.
[0120] However, it is preferable that the proportion by weight of
all C.sub.1-C.sub.4 alcohols other than ethanol in the solvent,
more preferably of all C.sub.1-C.sub.10 alcohols other than ethanol
in the solvent, is less than 50% by weight, based on the weight of
the ethanol encompassed by the solvent.
[0121] It is more preferable that the proportion by weight of all
C.sub.1-C.sub.4 alcohols other than ethanol in the solvent, more
preferably of all C.sub.1-C.sub.10 alcohols other than ethanol in
the solvent, is less than 25% by weight, based on the weight of the
ethanol encompassed by the solvent.
[0122] It is even more preferable that the proportion by weight of
all C.sub.1-C.sub.4 alcohols other than ethanol in the solvent,
more preferably of all C.sub.1-C.sub.10 alcohols other than ethanol
in the solvent, is less than 10% by weight, based on the weight of
the ethanol encompassed by the solvent.
[0123] It is yet more preferable that the proportion by weight of
all C.sub.1-C.sub.4 alcohols other than ethanol in the solvent,
more preferably of all C.sub.1-C.sub.10 alcohols other than ethanol
in the solvent, is less than 5% by weight, based on the weight of
the ethanol encompassed by the solvent.
[0124] It is even more preferable still that the proportion by
weight of all C.sub.1-C.sub.4 alcohols other than ethanol in the
solvent, more preferably of all C.sub.1-C.sub.10 alcohols other
than ethanol in the solvent, is less than 1% by weight, based on
the weight of the ethanol encompassed by the solvent.
[0125] The solvent is especially used in such an amount that the
weight of the solvent used is 1 to 5000 times, preferably 2.5 to
3000 times, more preferably 5 to 100 times and even more preferably
10-50 times the weight of the polymer P.sup.2 used.
[0126] Oxidizing agents used may likewise be the oxidizing agents
familiar to the person skilled in the art.
[0127] The oxidizing agent is especially selected from the group
consisting of peroxides, metal compounds, air, preferably
peroxides.
[0128] Peroxides are preferably selected from the group consisting
of hydrogen peroxide, performic acid, peracetic acid, perbenzoic
acid, perphthalic acid, meta-chloroperbenzoic acid. The most
preferred peroxide is hydrogen peroxide.
[0129] Metal compounds are preferably selected from the group
consisting of silver oxide, lead tetraacetate, potassium
hexacyanoferrate (III), potassium permanganate.
[0130] The reactant P.sup.2 used in the process according to the
invention can be obtained by prior art methods from commercially
available chemicals, for example 2,2,6,6-tetramethyl-4-piperidinyl
methacrylate. Such methods are described, for example, in EP 1 752
474 A1 or in European patent application 16172593.2. It is
accordingly also additionally possible to use crosslinkers as well
as the monomer in the synthesis of P.sup.2. Suitable crosslinkers
are compounds having more than one polymerizable group, the
crosslinker preferably being selected from the group consisting of
polyfunctional compounds based on (meth)acrylic acid,
polyfunctional compounds based on allyl ether, polyfunctional
compounds based on vinylic compounds. Polyfunctional compounds
based on (meth)acrylic acid are particularly preferred.
[0131] Polyfunctional compounds based on (meth)acrylic acid are
especially selected from ethylene glycol di(meth)acrylate,
diethylene glycol di(meth)acrylate, triethylene glycol
di(meth)acrylate, polyethylene glycol di(meth)acrylate,
propane-1,3-diol di(meth)acrylate, butane-2,3-diol
di(meth)acrylate, butane-1,4-diol di(meth)acrylate,
pentane-1,5-diol di(meth)acrylate, hexane-1,6-diol
di(meth)acrylate, heptane-1,7-diol di(meth)acrylate,
octane-1,8-diol di(meth)acrylate, nonane-1,9-diol di(meth)acrylate,
decane-1,10-diol di(meth)acrylate, trimethylolpropane
tri(meth)acrylate, glycerol di(meth)acrylate,
2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate.
[0132] The oxidizing agent is especially used in such an amount
that 1 to 40 mol, more preferably 1.5 to 15 mol, even more
preferably 5 to 14.4 mol, yet more preferably 13 to 14 mol and most
preferably 13 mol of the oxidizing agent are used per mole of NH
group to be oxidized in the polymer P.sup.2 used.
[0133] In the oxidation, it is additionally also possible to make
use of a catalyst. The catalysts used in the nitroxylation are
familiar to the person skilled in the art.
[0134] More particularly, nitroxylation can be accomplished using
catalysts selected from compounds of the metals of the chromium
group, especially molybdenum and tungsten. Preferably, the catalyst
used for nitroxylation is a compound of tungsten.
[0135] Compounds of tungsten are especially selected from the group
consisting of tungstic acid, tungstophosphoric acid, paratungstic
acid, tungstates, tungstophosphates, paratungstates, tungsten
oxides, tungsten carbonyls. Preferably, compounds of tungsten are
selected in accordance with the invention from alkali metal salts
and ammonium salts of the tungstates, more preferably from the
group consisting of ammonium tungstate, sodium tungstate, potassium
tungstate, even more preferably sodium tungstate.
[0136] Compounds of molybdenum are especially selected from the
group consisting of molybdic acid, molybdophosphoric acid,
paramolybdic acid, molybdates, molybdophosphates, paramolybdates,
molybdenum oxides, molybdenum carbonyls. Preferably, compounds of
molybdenum are selected in accordance with the invention from
alkali metal salts and ammonium salts of the molybdates, more
preferably from the group consisting of ammonium molybdate, sodium
molybdate, potassium molybdate, molybdenum trioxide, molybdenum
hexacarbonyl,
[0137] The catalyst is especially used in such an amount that 0.1
to 10 mol %, more preferably 1 to 5 mol %, even more preferably 2
to 3.5 mol % and even more preferably still 2.5 to 3.0 mol % of the
catalyst is used per mole of the compound of the structure (I) used
in step (a) of the process according to the invention.
[0138] The reaction time is likewise not particularly restricted,
and is especially 1 to 100 hours, preferably 3 to 96 hours, even
more preferably 10 to 96 hours, yet more preferably 25 to 96 hours,
even more preferably still 72 to 96 hours, most preferably 90 to 96
hours.
[0139] The polymer P.sup.1 obtained is then likewise isolated by
methods familiar to the person skilled in the art, such as
filtration and subsequent drying.
[0140] The end groups of the first repeat unit of the polymer
P.sup.1 which is present therefor in the chemical structure (I) at
the bonds defined by "#", and the end groups of the n.sup.1th
repeat unit of the polymer P.sup.1 according to the invention which
is present therefor in the chemical structure (I) at the bonds
defined by "##", are not particularly restricted and are a result
of the polymerization method used in the method for preparing the
polymer P.sup.1. Thus, they may be termination fragments of an
initiator or a repeat unit. Preferably, these end groups are
selected from hydrogen, halogen, hydroxyl, unsubstituted aliphatic
radical or aliphatic radical substituted by --ON, --OH, halogen
(which may especially be an unsubstituted or correspondingly
substituted alkyl group), (hetero)aromatic radical, which is
preferably a phenyl radical, benzyl radical or
.alpha.-hydroxybenzyl.
[0141] The end groups of the first repeat unit of the polymer
P.sup.2 which is present therefor in the chemical structure (II) at
the bonds defined by "#", and the end groups of the n.sup.2th
repeat unit of the polymer P.sup.2 according to the invention which
is present therefor in the chemical structure (II) at the bonds
defined by "##", are not particularly restricted and are a result
of the polymerization method used in the method for preparing the
polymer P.sup.2. Thus, they may be termination fragments of an
initiator or a repeat unit. Preferably, these end groups are
selected from hydrogen, halogen, hydroxyl, unsubstituted aliphatic
radical or aliphatic radical substituted by --ON, --OH, halogen
(which may especially be an unsubstituted or correspondingly
substituted alkyl group), (hetero)aromatic radical, which is
preferably a phenyl radical, benzyl radical or
.alpha.-hydroxybenzyl.
Definitions
[0142] In the context of this invention, some terms are defined as
follows:
[0143] "Nitroxyl" is a radical N O. function.
[0144] Nitroxylation is the oxidation of an NH group to a
nitroxyl.
[0145] "At least partly different from one another" means, in the
context of the invention, with regard to the polymer P.sup.1, that
at least two repeat units of the chemical structure (I) therein
differ from one another, and more particularly means that at least
two of the n mutually wined repeat units of the chemical structure
(I) differ in at least one of the R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, X, Y radicals.
[0146] "At least partly different from one another" means, in the
context of the invention, with regard to the polymer P.sup.2, that
at least two repeat units of the chemical structure (II) therein
differ from one another, and more particularly means that at least
two of the n mutually joined repeat units of the chemical structure
(II) differ in at least one of the R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, X, Y radicals.
[0147] The "degree of oxidation" of the polymer P.sup.1 (and if
appropriate also of the polymer P.sup.2) means the proportion of
nitroxyl groups, based on the sum total of all nitroxyl groups and
non-nitroxylated secondary NH groups. It is determined in
accordance with the invention by ESR. What is being determined here
is how many N O functions are present in the molecule being
examined in the particular case via the signal strength of the ESR
signal measured based on the amount of the particular polymer used.
The standard used in accordance with the invention is TEMPO
(2,2,6,6-tetramethylpiperidinyl-N-oxyl). Via the determination of
the number of N O. functions in the polymer P.sup.1 and the
comparison of the N O. functions in the polymer P.sup.2 used, it is
then possible to determine the degree of oxidation and hence the
efficiency of the process according to the invention.
[0148] "Halogenated hydrocarbons" are preferably selected from the
group consisting of dichloromethane, chloroform, dichloroethane.
Aliphatic nitriles are preferably selected from the group
consisting of acetonitrile, propionitrile, butyronitrile. Aromatic
nitriles are preferably selected from the group consisting of
benzonitrile, phenylacetonitrile. Alcohols other than ethanol are
preferably selected from the group consisting of methanol,
n-propanol, iso-propanol, n-butanol, sec-butanol, iso-butanol,
tert-butanol, preferably methanol. Aromatic hydrocarbons are
preferably selected from the group consisting of benzene,
toluene.
[0149] "C.sub.1-C.sub.4 alcohols" in accordance with the invention
are especially methanol, ethanol, n-propanol, iso-propanol,
n-butanol, sec-butanol, iso-butanol, tart-butanol.
[0150] "C.sub.1-C.sub.10 alcohols" in accordance with the invention
are especially methanol, ethanol, n-propanol, iso-propanol,
n-butanol, sec-butanol, iso-butanol, tert-butanol and all alcohols
having 5 to 10 carbon atoms.
[0151] "Substituted aliphatic radical" in the context of the
invention especially means that, in the aliphatic radical in
question, a hydrogen atom bonded to a carbon atom in the group in
question is replaced by a group selected from (hetero)aromatic
radical, --NO.sub.2, --ON, --F, --Cl, --Br, --I,
--C(.dbd.O)NR.sup.IR.sup.II, --NR.sup.IIIR.sup.IV,
--C(.dbd.O)OR.sup.V, preferably --NO.sub.2, --CN, --F, --Cl, --Br,
--I, even more preferably --F, --Cl, --Br, --I, most preferably
--F, --Cl, --Br, where R.sup.I, R.sup.II, R.sup.III, R.sup.IV,
R.sup.V are selected from H, alkyl, haloalkyl, aromatic,
heteroaromatic, and where in the case that R.sup.Iv=alkyl or
haloalkyl may also be --O.sup.-.
[0152] An optionally substituted aliphatic radical is preferably
unsubstituted.
[0153] An optionally substituted alkylene radical is preferably
unsubstituted.
[0154] An alkylene radical having 1 to 10 carbon atoms especially
has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms and even
more preferably 1 to 3 carbon atoms, and is most preferably
methylene, ethylene or n-propylene.
[0155] An alkyl group having 1 to 10 carbon atoms especially has 1
to 6 carbon atoms, preferably 1 to 4 carbon atoms and even more
preferably 1 to 3 carbon atoms, and is most preferably methyl,
ethyl or n-propyl.
[0156] A (hetero)aromatic radical in the context of the invention s
a heteroaromatic or aromatic radical. A (hetero)aromatic radical
may be monovalent, i.e. may be bonded to the rest of the molecule
via just one of its carbon atoms (in the case of an aromatic
radical) or via one of its carbon atoms or heteroatoms (in the case
of a heteroaromatic radical).
[0157] A (hetero)aromatic radical may alternatively be divalent,
i.e. may be bonded to the rest of the molecule via two of its
carbon atoms (in the case of an aromatic radical) or may be bonded
to the rest of the molecule via two of its carbon atoms, two of its
heteroatoms or one of its carbon atoms and one of its heteroatoms
(in the case of a heteroaromatic radical).
[0158] When they are not referred to explicitly as divalent in this
invention, the term "(hetero)aromatic radical" in the context of
the invention shall be understood to mean monovalent
(hetero)aromatic radicals.
[0159] An aromatic radical has exclusively carbon atoms and at
least one aromatic ring. An aromatic radical is especially selected
from aryl radical, aralkyl radical, alkaryl radical. Aryl radicals
have exclusively aromatic rings and are joined to the molecule via
a carbon atom in the aromatic ring. An aryl radical is preferably
phenyl.
[0160] Alkaryl radicals have at least one aromatic ring via which
they are joined to the rest of the molecule and additionally also
bear alkyl radicals on the aromatic ring. An alkaryl radical is
preferably tolyl.
[0161] Aralkyl radicals are formally derived by replacement of a
hydrocarbyl radical of an alkyl group with an aryl group or an
alkaryl group. An alkaryl radical is preferably benzyl,
phenylethyl, .alpha.-methylbenzyl.
[0162] A heteroaromatic radical is especially selected from
heteroaryl radical, heteroaralkyl radical, alkylheteroaryl radical.
It is an aromatic radical which additionally has at least one
heteroatom, especially a heteroatom selected from the group
consisting of nitrogen, oxygen, sulphur, within the aromatic ring
or, in the case of a heteroaralkyl radical or of an alkylheteroaryl
radical, alternatively or additionally outside the aromatic
ring.
[0163] Preferred (hetero)aromatic radicals are selected from the
group consisting of a ring of the above-defined chemical structure
(III), azole, imidazole, pyrrole, pyrazole, triazole, tetrazole,
thiophene, furan, thiazole, thiadiazole, oxazole, oxadiazole,
pyridine, pyrimidine, triazine, tetrazine, thiazine, benzofuran,
purine, indole, 9-anthryl, 9-phenanthryl.
[0164] A divalent (hetero)aromatic radical in the context of the
invention is a divalent aromatic radical or a divalent
heteroaromatic radical, preferably a divalent aromatic radical.
[0165] According to the invention, a divalent aromatic radical is a
divalent hydrocarbyl group having at least 6 and preferably 6 to 30
carbon atoms, of which at least 6 carbon atoms are present in an
aromatic system and the other carbon atoms, if present, are
saturated. The divalent aromatic radical may be joined to the rest
of the molecule via carbon atoms in the aromatic system or, if
present, saturated carbon atoms.
[0166] Preferably, a divalent aromatic radical is a chemical
structure (d)
##STR00013##
[0167] where y' is an integer >0, preferably from 0 to 24; where
y'' is an integer >0, preferably from 0 to 24; and where
preferably, at the same time, y' y''.ltoreq.24.
[0168] A divalent heteroaromatic radical is a divalent aromatic
radical which additionally has at least one heteroatom, especially
at least one heteroatom selected from the group consisting of
nitrogen, oxygen, sulphur, within or outside the aromatic ring,
preferably within the aromatic ring, but is especially joined to
the rest of the molecule via carbon atoms.
[0169] "Optionally substituted (hetero)aromatic radical" especially
denotes unsubstituted (hetero)aromatic radical and preferably
unsubstituted aromatic radical.
[0170] "Substituted or unsubstituted (hetero)aromatic radical"
especially denotes unsubstituted (hetero)aromatic radical and
preferably unsubstituted aromatic radical.
[0171] "Substituted (hetero)aromatic radical" in the context of the
invention especially means that, in the (hetero)aromatic radical in
question, a hydrogen atom bonded to a carbon atom in the group in
question is replaced by a group selected from alkyl group, alkenyl
group, alkynyl group, haloalkyl group, --NO.sub.2, --ON, --F, --Cl,
--Br, --C(.dbd.O)NR.sup.IR.sup.II, --NR.sup.IIIR.sup.V, preferably
--NO.sub.2, --ON, --F, --Cl, alkyl group having 1 to 10 carbon
atoms, alkenyl group having 2 to 10 carbon atoms, where R.sup.I,
R.sup.II, R.sup.III, R.sup.V are selected from H, alkyl group
having preferably 1 to 10 carbon atoms, alkenyl group having 2 to
10 carbon atoms, haloalkyl group having preferably 1 to 10 carbon
atoms, aromatic, heteroaromatic, and where R.sup.III in the case
that R.sup.V=alkyl or haloalkyl may also be --O.sup.-.
[0172] "Where the optionally substituted aliphatic radical may
additionally have at least one group selected from ether,
thioether, optionally nitroxylated amino ether, carbonyl group,
carboxylic ester group, carboxamide group, sulphonic ester group,
phosphoric ester" means:
[0173] In the case of ether, that an --O-- group is present in the
optionally substituted aliphatic radical at least between two
sp.sup.3-hybridized carbon atoms of the aliphatic radical,
preferably between two --CH.sub.2-- groups of the aliphatic
radical, even more preferably between two --CH.sub.2CH.sub.2--
groups of the aliphatic radical.
[0174] In the case of thioether, that an --S-- group is present in
the optionally substituted aliphatic radical at least between two
sp.sup.3-hybridized carbon atoms of the aliphatic radical,
preferably between two --CH.sub.2-- groups of the aliphatic
radical, even more preferably between two --CH.sub.2CH.sub.2--
groups of the aliphatic radical.
[0175] In the case of the optionally nitroxylated amino ether, that
an --NR'-- with R'.dbd.H, --O. group or alkyl having 1 to 10 carbon
atoms, preferably R'.dbd.H or alkyl having 1 to 10 carbon atoms, is
present in the optionally substituted aliphatic radical at least
between two sp.sup.3-hybridized carbon atoms of the aliphatic
radical, preferably between two --CH.sub.2-- groups of the
aliphatic radical, even more preferably between two
--CH.sub.2CH.sub.2-- groups of the aliphatic radical.
[0176] In the case of the carbonyl group, that a --C(.dbd.O)--
group is present in the optionally substituted aliphatic radical at
least between two sp.sup.3-hybridized carbon atoms of the aliphatic
radical, preferably between two --CH.sub.2-- groups of the
aliphatic radical, even more preferably between two
--CH.sub.2CH.sub.2-- groups of the aliphatic radical.
[0177] In the case of the carboxylic ester group, that a
--C(.dbd.O)--O-- group is present in the optionally substituted
aliphatic radical at least between two sp.sup.3-hybridized carbon
atoms of the aliphatic radical, preferably between two --CH.sub.2--
groups of the aliphatic radical, even more preferably between two
--CH.sub.2CH.sub.2-- groups of the aliphatic radical.
[0178] In the case of the carboxamide group, that a
--C(.dbd.O)--NU-- group with U.dbd.H or alkyl having 1 to 10 carbon
atoms is present in the optionally substituted aliphatic radical at
least between two sp.sup.3-hybridized carbon atoms of the aliphatic
radical, preferably between two --CH.sub.2-- groups of the
aliphatic radical, even more preferably between two
--CH.sub.2CH.sub.2-- groups of the aliphatic radical.
[0179] In the case of the sulphonic ester group, that an
--S(O).sub.2O-- group is present in the optionally substituted
aliphatic radical at least between two sp.sup.3-hybridized carbon
atoms of the aliphatic radical, preferably between two --CH.sub.2--
groups of the aliphatic radical, even more preferably between two
--CH.sub.2CH.sub.2-- groups of the aliphatic radical.
[0180] In the case of the phosphoric ester group, that a group
selected from -OP(.dbd.O)(O.sup.-(W.sup.d+).sub.1/z)-O--,
--OP(.dbd.O)(OR'')--O-- where R''.dbd.H or alkyl group having 1 to
10 carbon atoms is present in the optionally substituted aliphatic
radical at least between two sp.sup.3-hybridized carbon atoms of
the aliphatic radical, preferably between two --CH.sub.2-- groups
of the aliphatic radical, even more preferably between two
--CH.sub.2CH.sub.2-- groups of the aliphatic radical.
[0181] In this case, W.sup.d+ is selected from the group consisting
of alkali metal cation, where the alkali metal cation is preferably
selected from the group consisting of Li.sup.+, Na.sup.+, K.sup.+,
alkaline earth metal cation, where the alkaline earth metal cation
is preferably selected from the group consisting of Mg.sup.2+,
Ca.sup.2+, transition metal cation, where the transition metal
cation is preferably selected from the group consisting of iron
cation, zinc cation, mercury cation, nickel cation, cadmium cation,
and from tetraalkylammonium cation, imidazolium cation,
monoalkylimidazolium cation, dialkylirnidazolium cation, where the
alkyl groups in the tetraalkylammonium cation,
rnonoalkylimidazolium cation, dialkylimidazolium cation each
independently preferably have 1 to 30 carbon atoms. Moreover, d
indicates the number of positive charges of W.sup.d+.
[0182] Preferably, W.sup.d+ is selected from the group consisting
of Li.sup.+, Na.sup.+, K.sup.+, Mg.sup.2+, Ca.sup.2+, Zn.sup.2+,
Fe.sup.2+, Fe.sup.3+. Cd.sup.2+, Hg.sup.+, Hg.sup.2+, Ni.sup.2+,
Ni.sup.3+, Ni.sup.4+,
[0183] where d in the case of each of Li.sup.+, Na.sup.+, K.sup.+,
Hg.sup.+=1,
[0184] where d in the case of each of Mg.sup.2+, Ca.sup.2+,
Zn.sup.2+, Cd.sup.2+, Hg.sup.2+, Ni.sup.2+, Fe.sup.2+=2,
[0185] where d in the case of Fe.sup.3+, Ni.sup.3+=3,
[0186] where d in the case of Ni.sup.4+=4.
[0187] Fields of Use of the Polymer P.sup.1 Prepared by the Process
According to the Invention
[0188] The polymer P.sup.1 is especially suitable for use as
redox-active electrode material in an electrical charge storage
means, preferably for storage of electrical energy, and more
preferably as a positive electrode element.
[0189] More preferably, the redox-active electrode material takes
the form of an at least partial surface coating of electrode
elements for electrical charge storage means, especially secondary
batteries. Electrode elements here comprise at least one surface
layer and one substrate.
[0190] A redox-active material for storage at electrical energy is
a material which can store electrical charge and release it again,
for example by accepting and releasing electrons. This material can
be used, for example, as an active electrode material in an
electrical charge storage means. Such electrical charge storage
means for storage of electrical energy are especially selected from
the group consisting of secondary batteries (also called
"accumulators"), redox flow batteries, supercapacitors, and are
preferably secondary batteries.
[0191] Preferably, the electrical charge storage means is a
secondary battery. A secondary battery comprises a negative
electrode and a positive electrode which are separated from one
another by a separator, and an electrolyte which surrounds the
electrodes and the separator.
[0192] The separator is a porous layer which is ion-permeable and
enables the balancing of the charge. The task of the separator is
to separate the positive electrode from the negative electrode and
to enable balancing of charge through permutation of ions. The
separator used in the secondary battery is especially a porous
material, preferably a membrane consisting of a polymeric compound,
for example polyolefin, polyamide or polyester. In addition, it is
possible to use separators made from porous ceramic materials.
[0193] The main task of the electrolyte is to assure ion
conductivity, which is needed to balance the charge. The
electrolyte of the secondary battery may be either a liquid or an
oligomeric or polymeric compound having high ion conductivity ("gel
electrolyte" or "solid state electrolyte"). Preference is given,
however, to an oligomeric or polymeric compound.
[0194] If the electrolyte is liquid, it is especially composed of
one or more solvents and one or more conductive salts.
[0195] The solvent of the electrolytes preferably independently
comprises one or more solvents having a high boiling point and high
ion conductivity but low viscosity, for example acetonitrile,
dimethyl sulphoxide, ethylene carbonate, propylene carbonate,
dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate,
.gamma.-butyrolactone, tetrahydrofuran, dioxolane,
1,2-dimethoxyethane, 1,2-diethoxyethane, diglyme, triglyme,
tetraglyme, ethyl acetate, 1,3-dioxolane or water.
[0196] The conductive salt in the electrolyte consists of a cation
of the formula Me.sup.e+ and an anion of the formula An.sup.f- in
the formula (M.sup.e+).sub.a(An.sup.f-).sub.b where e and f are
integers depending on the charge of M and An; a and b are integers
which represent the molecular composition of the conductive salt.
Cations used in the abovementioned conductive salt are positively
charged ions, preferably metals of the first and second main
groups, for example lithium, sodium, potassium or magnesium, but
also other metals of the transition groups, such as zinc, and
organic cations, for example quaternary ammonium compounds such as
tetraalkylammonium compounds. The preferred cation is lithium.
[0197] Anions used in said conductive salt are preferably inorganic
anions such as hexafluorophosphate, tetrafluoroborate, triflate,
hexafluoroarsenate, hexafluoroantimonate, tetrafluoroaluminate,
tetrafluoroindate, perchlorate, bis(oxalato)borate,
tetrachloroaluminate, tetrachlorogallate, but also organic anions,
for example N(CF.sub.3SO.sub.2).sub.2.sub.-,
CF.sub.3SO.sub.3.sub.-, alkoxides, for example tert-butoxide or
iso-propoxide, but also halides such as fluoride, chloride, bromide
and iodide. The preferred anion is perchlorate,
ClO.sub.4.sub.-.
[0198] The preferred conductive salt is thus LiClO.sub.4.
[0199] If ionic liquids are used, they can be used either as
solvent of the electrolyte, as conductive salt, or else as complete
electrolyte.
[0200] In the embodiment in which the redox-active electrode
material takes the form of an at least partial surface coating of
electrode elements for electrical charge storage means, especially
secondary batteries, an electrode element has an at least partial
layer on a substrate surface. This layer especially comprises a
composition comprising the polymer according to the invention as
redox-active material for charge storage and especially at least
also a conductivity additive and especially also at least one
binder additive.
[0201] The application of this composition (another expression for
composition: "composite") on the substrate is possible by means of
methods known to those skilled in the art. More particularly, the
polymer according to the invention is applied on the substrate with
the aid of an electrode slurry. The substrate of the electrode
element is especially selected from conductive materials,
preferably metals, carbon materials, oxide substances.
[0202] Preferred metals are selected from platinum, gold, iron,
copper, aluminium or a combination of these metals. Preferred
carbon materials are selected from glassy carbon, graphite film,
graphene, carbon sheets. Preferred oxide substances are, for
example, selected from the group consisting of indium tin oxide
(ITO), indium zinc oxide (IZO), antimony zinc oxide (AZO), fluorine
tin oxide (FTO) or antimony tin oxide (ATO).
[0203] The surface layer of the electrode element comprises at
least the polymer according to the invention as redox-active
material for charge storage and especially at least a conductivity
additive and a binder additive.
[0204] The conductivity additive is especially at least one
electrically conductive material, preferably selected from the
group consisting of carbon materials, electrically conductive
polymers, and especially carbon materials. Carbon materials are
especially selected from the group consisting of carbon platelets,
carbon fibres, carbon nanotubes, graphite, carbon black, graphene,
and are more preferably carbon fibres. Electrically conductive
polymers are especially selected from the group consisting of
polyanilines, polythiophenes, polyacetylenes,
poly(3,4-ethylenedioxythiophene) polystyrenesulphonate
(=PEDOT:PSS), polyarcenes.
[0205] Binder additives are especially materials having binder
properties and are preferably polymers selected from the group
consisting of polytetrafluoroethylene, polyvinylidene fluoride,
polyhexafluoropropylene, polyvinyl chloride, polycarbonate,
polystyrene, polyacrylates, polymethacrylates, polysulphones,
cellulose derivatives, polyurethanes.
[0206] The polymer P.sup.2 is especially applied to the substrate
of the electrode element in an electrode slurry.
[0207] The electrode slurry is a solution or suspension and
comprises the polymer according to the invention and especially the
above-described conductivity additive and the above-described
binder additive.
[0208] The electrode slurry preferably comprises a solvent and
further constituents comprising redox-active material for storage
of electrical energy (which is especially the polymer according to
the invention), and preferably also the conductivity additive and
the binder additive.
[0209] In the further constituents, preferably, the proportion of
the redox-active material for storage of electrical energy (which
is especially the polymer according to the invention) is from 5 to
100 percent by weight, the proportion of the conductivity additive
from 0 to 80 and preferably 5 to 80 percent by weight, and the
proportion of binder additive from 0 to 10 and preferably 1 to 10
percent by weight, where the sum total is 100 percent by
weight.
[0210] Solvents used for the electrode slurry are independently one
or more solvents, preferably solvents having a high boiling point,
more preferably selected from the group consisting of
N-methyl-2-pyrrolidone, water, dimethyl sulphoxide, ethylene
carbonate, propylene carbonate, dimethyl carbonate, methyl ethyl
carbonate, .alpha.-butyrolactone, tetrahydrofuran, dioxolane,
sulpholane, N,N'-dimethylformamide, N,N'-dimethylacetarnide. The
concentration of the redox-active material, especially of the
polymer according to the invention for storage of electrical energy
in the above mentioned electrode slurry is preferably between 0.1
and 10 mg/ml, more preferably between 0.5 and 5 mg/ml.
[0211] If the polymer of this invention as redox-active material is
used as positive electrode element for electrical charge storage
means, the redox-active material used for electrical charge storage
in the negative electrode is a material which exhibits a redox
reaction at a lower electrochemical potential than the polymer of
this invention. Preference is given to those materials selected
from the group consisting of carbon materials, which are especially
selected from the group consisting of graphite, graphene, carbon
black, carbon fibres, carbon nanotubes, metals or alloys, which are
especially selected from the group consisting of lithium, sodium,
magnesium, lithium-aluminium, Li--Si, Li--Sn, Li--Ti, Si, SiO,
SiO.sub.2, Si--SiO.sub.2 complex, Zn, Sn, SnO, SnO.sub.2, PbO,
PbO.sub.2, GeO, GeO.sub.2, WO.sub.2, MoO.sub.2, Fe.sub.2O.sub.3,
Nb.sub.2O.sub.5, TiO.sub.2, Li.sub.4Ti.sub.5O.sub.12, and
Li.sub.2Ti.sub.3O.sub.7, and organic redox-active materials.
Examples of organic redox-active materials are compounds having a
stable organic radical, compounds having an organosulphur unit,
having a quinone structure, compounds having a dione system,
conjugated carboxylic acids and salts thereof, compounds having a
phthalimide or naphthalimide structure, compounds having a
disulphide bond and compounds having a phenanthrene structure and
derivatives thereof. If an abovementioned redox-active oligomeric
or polymeric compound is used in the negative electrode, this
compound may also be a composite, i.e, a composition, consisting of
this oligomeric or polymeric compound, a conductivity additive and
a binder additive in any ratio. The conductivity additive in this
case too is especially at least one electrically conductive
material, preferably selected from the group consisting of carbon
materials, electrically conductive polymers, and especially carbon
materials. Carbon materials are especially selected from the group
consisting of carbon fibres, carbon nanotubes, graphite, carbon
black, graphene, and are more preferably carbon fibres.
Electrically conductive polymers are especially selected from the
group consisting of polyanilines, polythiophenes, polyacetylenes,
poly(3,4-ethylenedioxythiophene) polystyrenesulphonate
"PEDOT:PSS"), polyarcenes. Binder additives in this case too are
especially materials having binder properties and are preferably
polymers selected from the group consisting of
polytetrafluoroethylene, polyvinylidene fluoride,
polyhexafluoropropyiene, polyvinyl chloride, polycarbonate,
polystyrene, polyacrylates, polymethacrylates, polysulphones,
cellulose derivatives, polyurethanes.
[0212] This composite may, as described above, be present as a
layer on a substrate through a known film-forming process with the
aid of an electrode slurry.
[0213] The examples which follow are intended to further elucidate
the invention, but without restricting it thereto.
EXAMPLES
[0214] I. Chemicals Used
[0215] 2,2,6,6-Tetramethyl-4-piperidinyl methacrylate (CAS number:
31582-45-3; melting point 61.degree. C., abbreviated hereinafter as
"TAA-of-MA") was synthesized by prior art methods.
[0216] Ethylene glycol dimethacrylate (CAS number: 97-90-5) was
obtained from Evonik.
[0217] Ammonium peroxodisulphate (CAS number: 7727-54-0) was
obtained from Sigma Aldrich.
[0218] Polyoxyethylene nonylphenyl ether (CAS number: 68412-54-4)
was obtained from Sigma Aldrich.
[0219] Sodium dodecylbenzenesulphonate (CAS number: 25155-30-0) was
obtained from Sigma Aldrich.
[0220] 4,4'-Azobis(4-cyanovaleric acid) (CAS number: 2638-94-0) was
obtained from Wako V-501 # AWL2803.
[0221] Sodium tungstate dihydrate (CAS number: 10213-10-2) was
obtained from Sigma Aldrich.
[0222] Ethylenediaminetetraacetic acid (abbreviated hereinafter as
"EDTA"; CAS number: 60-00-4) was obtained from Roth.
[0223] TEMPO (2,2,6,6,-Tetramethylpiperidinyl-N-oxyl; CAS number:
2564-83-2) was obtained from Sigma-Aldrich.
[0224] II. Polymerization of TAA-ol to
poly(2.2.6,6-tetramethylpiperidinyloxylmethacrylate) 1
[0225] 150.0 g of TAA-ol-MA (melting point 61.degree. C.), 1 g of a
mixture of 2 parts sodium dodecylbenzenesulphonate and 1 part
polyoxyethylene nonylphenyl ether and 2.7 g of ethylene glycol
dimethacrylate were added to 467 ml of water in a 1 I jacketed
reactor with stirrer and condenser, and heated to 65.degree. C.,
Thereafter, the mixture was dispersed at 6000 rpm for 15 min with
an Ultraturrax (machine: Ultra-Turrax T series disperser; from
IKA-Werke GmbH and Co. KG; model: T 25 D; dispersion tool: S 25
N-25 G) and then while cooling to 40.degree. C. over 30
minutes.
[0226] The dispersion thus obtained was transferred into a reactor,
and equilibrated further therein to 40.degree. C. The dispersion
was placed under a nitrogen blanket and the passage of nitrogen was
continued during the reaction that followed. Thereafter, 0.27 g of
ammonium peroxodisulphate was added and the mixture was stirred
overnight at a temperature between 40.degree. C. and 45.degree. C.
To complete the reaction, the mixture was then polymerized at
65.degree. C. for another 1 hour. Then the solution was cooled to
room temperature.
[0227] The quantitative yield of polymer 1 corresponded to 90%, The
polymer 1 was in the form of a finely distributed precipitate in
the reactor and could be filtered and isolated without any
problem.
III. Comparative Experiments C.sub.1 to C.sub.6 and Inventive
Experiments I1 to I3: Oxidation of 1 to
poly(2.2.6,6-tetramethylpiperidinyloxylmethacrylate) 2
[0228] 40 g of polymer 1 obtained as described in section II were
converted to a slurry in a flask with 20 g of water. The
temperature of the flask was adjusted by means of a water bath or
ice bath to room temperature (=25.degree. C.; C2, C4, C5, C6) or
1.degree. C. (C1, C3, 11, 13). While stirring with a stirrer motor,
80 g of water (C1, C2), of a mixture of water with methanol (C3,
C4), of ethanol (C5, C6), or of a mixture of water with ethanol
(I1, I2, I3), were then added. In the case of comparative
experiments C5 and C6, for establishment of the desired ratio of
ethanol and water, the corresponding proportion of the water used
to form the slurry was removed prior to addition of the ethanol. In
the case of comparative experiment C3 and of inventive experiments
I1 and I3, after addition of the alcoholic solution, the suspension
obtained was cooled to 0.degree. C. (C3, I1) or with a coolant
mixture to .about.-12.degree. C. (I3). The suspension thus obtained
was then stirred for a further 30 minutes, in order to allow the
polymer to swell.
[0229] This was followed by the addition of 1.76 g of sodium
tungstate dihydrate and 0.45 g of EDTA. After .about.1 minute, for
oxidation, firstly 27.2 g of 30% aqueous hydrogen peroxide solution
was then added in portions, followed after a further half an hour
by 27.2 g of 50% aqueous hydrogen peroxide solution. The mixture
was then stirred at the temperature T.sub.1 specified in the table
in section V for 90 hours and, toward the end, heated to 40.degree.
C. for another 1 hour in each case.
[0230] Thereafter, the reaction mixture was cooled, filtered
through a fluted filter, washed three times with 50 g of water and
then put in a vacuum drying cabinet overnight. The completeness of
the oxidation (degree of oxidation=proportion of secondary NH
groups that have been oxidized to N .COPYRGT.) was determined by
means of ESR.
IV. ESR Analysis
[0231] Electron spin resonance spectra were recorded by means of a
spin EMXmicro CW-EPR spectrometer (EMX micro EMM-6/1/9-VT control
unit, ER 070 magnet, EMX premium ER04 X-band microwave bridge,
equipped with a EMX standard resonator, EMX080 power unit) from
Bruker Corporation. The samples were analysed at room temperature
and quantitatively evaluated with the Bruker Xenon software
package, version 1.1 b86. The SpinCount.TM. software module. The
spectrometer was calibrated with TEMPO (99% purity, Sigma-Aldrich
Chemie GmbH) as reference. No internal reference was present during
the sample measurement. Three samples were analysed for each
substance.
V. Results
[0232] The following table states the ratio of water and
methanol/ethanol that was present in the solution during the
oxidation, what temperature was utilized in the oxidation and how
high the degree of oxidation determined by means of ESR was:
TABLE-US-00001 Solvents used Ratio of Temperature Degree of
Experiment H.sub.2O Methanol Ethanol water:alcohol T.sub.1
oxidation C1 x -- -- -- 1.degree. C. 81% C2 x -- -- -- 25.degree.
C. 96% C3 x x -- 7.1:1 0.degree. C. 88% C4 x x -- 7.1:1 25.degree.
C. 96% C5 x x 0.75:1 25.degree. C. 96.6%.sup. C6 x x 0.75:1
25.degree. C. 95.2%.sup. I1 x -- x 7.1:1 0.degree. C. 98% I2 x -- x
7.1:1 25.degree. C. 98% I3 x -- x 1.1:1 ~-12.degree. C.
98.4%.sup.
VI. Results
[0233] As apparent from the table shown in point V, a better degree
of oxidation is achieved when a mixture of ethanol and water is
used compared to water (C1, C2) or a mixture of water with methanol
(C3, C4). However, this effect was observed only for those solvents
in which ethanol is present in deficiency in relation to water, as
apparent from the comparison of comparative examples C5 and C6 with
inventive examples I1, I2 and I3.
[0234] The degree of oxidation of 98% or 98.4% observed in
inventive examples I1, I2 and I3 is higher than that described in
the prior art (page 8 line 33 of EP 1 911 775 A1 describes a
conversion efficiency of 95.5%).
[0235] This result, namely that such a high degree of oxidation can
be observed in an aqueous solvent containing ethanol in deficiency
relative to water, is completely surprising.
* * * * *