U.S. patent application number 09/829479 was filed with the patent office on 2001-11-08 for polymerizable compositions containing alkoxyamine compounds derived from nitroso- or nitrone compounds.
Invention is credited to Kramer, Andreas, Nesvadba, Peter, Stauffer, Werner, Steinmann, Alfred.
Application Number | 20010039315 09/829479 |
Document ID | / |
Family ID | 26148048 |
Filed Date | 2001-11-08 |
United States Patent
Application |
20010039315 |
Kind Code |
A1 |
Nesvadba, Peter ; et
al. |
November 8, 2001 |
Polymerizable compositions containing alkoxyamine compounds derived
from nitroso- or nitrone compounds
Abstract
A polymerizable composition, comprising a) at least one
ethylenically unsaturated monomer or oligomer, and b) an initiator
compound of formula (I) 1 wherein n is 0 or 1. The compounds of
formula (I) are prepared from a free radical 2 and a compound of
formula R.sub.10NO or 3 Further aspects of the present invention
are a process for polymerizing ethylenically unsaturated monomers,
novel initiator compounds and their use for polymerization,
intermediate compounds and also the polymer or copolymer produced
by this process.
Inventors: |
Nesvadba, Peter; (Marly,
CH) ; Kramer, Andreas; (Dudingen, CH) ;
Steinmann, Alfred; (Praroman, CH) ; Stauffer,
Werner; (Fribourg, CH) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
26148048 |
Appl. No.: |
09/829479 |
Filed: |
April 9, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09829479 |
Apr 9, 2001 |
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09114621 |
Jul 13, 1998 |
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6262206 |
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Current U.S.
Class: |
525/374 ;
526/220; 568/949 |
Current CPC
Class: |
C07D 207/20 20130101;
C07D 207/09 20130101; C07C 255/64 20130101; C08F 293/00 20130101;
C07C 2601/14 20170501; C08F 4/00 20130101 |
Class at
Publication: |
525/374 ;
568/949; 526/220 |
International
Class: |
C07C 207/00; C08F
004/32; C08F 010/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 15, 1997 |
EP |
97810487.5 |
Jul 15, 1997 |
EP |
97810488.3 |
Claims
What is claimed is:
1. A polymerizable composition, comprising a) at least one
ethylenically unsaturated monomer or oligomer, and b) an initiator
compound of formula (1) 40wherein n is 0 or 1 R.sub.1, R.sub.2,
R.sub.3 are each independently of one another hydrogen, halogen,
NO.sub.2, cyano, --CONR.sub.5R.sub.6, --(R.sub.9)COOR.sub.4,
--C(O)--R.sub.7, --OR.sub.8, --SR.sub.8, --NHR.sub.8,
--N(R.sub.8).sub.2, carbamoyl, di(C.sub.1-C.sub.18alkyl)carbamoyl,
--C(.dbd.NR.sub.5)(NHR.sub.6); unsubstituted C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom; or C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkenyl,
C.sub.2-C.sub.18alkynyl, C.sub.7-C.sub.9phenylal- kyl,
C.sub.3-C.sub.12cycloalkyl or C.sub.3-C.sub.12cycloalkyl containing
at least one nitrogen or oxygen atom, which are substituted by
NO.sub.2, halogen, amino, hydroxy, cyano, carboxy,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or
phenyl, naphthyl, which are unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, halogen, cyano, hydroxy, carboxy,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or
R.sub.2 and R.sub.3, together with the linking carbon atom, form a
C.sub.3-C.sub.12 cycloalkyl radical, a
(C.sub.4-C.sub.12cycloalkanon)-yl radical or a
C.sub.3-C.sub.12cycloalkyl radical containing at least one O atom
and/or a NR.sub.8 group; or if n is 1 41R.sub.4 is hydrogen,
C.sub.1-C.sub.18alkyl, phenyl, an alkali metal cation or a
tetraalkylammonium cation; R.sub.5 and R.sub.6 are hydrogen,
C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkyl which is substituted
by at least one hydroxy group or, taken together, form a
C.sub.2-C.sub.12alkylene bridge or a C.sub.2-C.sub.12-alkylene
bridge interrupted by at least one O or/and NR.sub.8 atom; R.sub.7
is hydrogen, C.sub.1-C.sub.18alkyl or phenyl; R.sub.8 is hydrogen,
C.sub.1-C.sub.18alkyl or C.sub.2-C.sub.18alkyl which is substituted
by at least one hydroxy group; R.sub.9 is C.sub.1-C.sub.12alkylen
or a direct bond; R.sub.10 is C.sub.4-C.sub.18alkyl bound via a
tertiary C-atom to the nitrogen atom, C.sub.9-C.sub.11phenylalkyl,
C.sub.3-C.sub.12cycloalky- l or C.sub.3-C.sub.12cycloalkyl
containing at least one nitrogen or oxygen atom; or
C.sub.4-C.sub.18alkyl bound via a tertiary C-atom to the nitrogen
atom, C.sub.9-C.sub.11phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom, which are substituted by NO.sub.2, halogen, amino,
hydroxy, cyano, carboxy, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or phenyl, naphthyl, which are
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio, halogen, cyano,
hydroxy, carboxy, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; if n is 1 R.sub.11 is
C.sub.1-C.sub.18alkyl, C.sub.7-C.sub.9phenylalkyl,
C.sub.3-C.sub.12cycloalkyl or C.sub.3-C.sub.12cycloalkyl containing
at least one nitrogen or oxygen atom; or C.sub.1-C.sub.18alkyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom, which are substituted by NO.sub.2, halogen, amino,
hydroxy, cyano, carboxy, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or phenyl, naphthyl, which are
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio, halogen, cyano,
hydroxy, carboxy, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or a polycyclic cycloaliphatic ring
system or a polycyclic cycloaliphatic ring system with at least one
di- or trivalent nitrogen atom; or R.sub.10 and R.sub.11 together
form a C.sub.2-C.sub.12alkylene bridge, a
C.sub.3-C.sub.12alkylen-on bridge or a C.sub.2-C.sub.12alkylene
bridge which is interrupted by at least one O or N atom, which
bridges are unsubstituted or substituted with
C.sub.1-C.sub.18alkyl, hydroxy(C.sub.1-C.sub.4)alkyl, phenyl,
C.sub.7-C.sub.9phenylalkyl, NO.sub.2, halogen, amino, hydroxy,
cyano, carboxy, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino,
R.sub.12 is hydrogen, --(R.sub.9)COOR.sub.4, cyano, --OR.sub.8,
--SR.sub.8, --NHR.sub.8, --N(R.sub.8).sub.2, --NH--C(O)--R.sub.8,
unsubstituted C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkenyl,
C.sub.2-C.sub.18alkynyl, C.sub.7-C.sub.9phenylalkyl,
C.sub.3-C.sub.12cycloalkyl or C.sub.3-C.sub.12cycloalkyl containing
at least one nitrogen or oxygen atom; or C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18 alkynyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom, which are substituted by NO.sub.2, halogen, amino,
hydroxy, cyano, carboxy, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or phenyl, naphthyl, which are
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio, halogen, cyano,
hydroxy, carboxy, C.sub.1-C.sub.4alkylamino,
di(C.sub.1-C.sub.4alkyl)amino; or R.sub.11 and R.sub.12 together
with the linking carbon atom form a C.sub.3-C.sub.12cycloalkyl
radical; with the proviso that
bis-(2-cyano-2-propyl)-N-phenylhydroxylamine is excluded and if n=0
R.sub.10 is different from the group --CR.sub.1R.sub.2R.sub.3.
2. A composition according to claim 1, which additionally comprises
a solvent selected from the group consisting of water, alcohols,
esters, ethers, ketones, amides, sulfoxides, hydrocarbons and
halogenated hydrocarbons.
3. A composition according to claim 1, wherein the ethylenically
unsaturated monomer or oligomer is selected from the group
consisting of styrene, substituted styrene, conjugated dienes,
acrolein, vinyl acetate, (alkyl)acrylic acidanhydrides,
(alkyl)acrylic acid salts, (alkyl)acrylic esters or
(alkyl)acrylamides.
4. A composition according to claim 3 wherein the ethylenically
unsaturated monomer is styrene, a-methyl styrene, p-methyl styrene
or a compound of formula
CH.sub.2.dbd.C(R.sub.a)--(C.dbd.Z)--R.sub.b, wherein R.sub.a is
hydrogen or C.sub.1-C.sub.4alkyl, R.sub.b is NH.sub.2, O(Me),
glycidyl, unsubstituted C.sub.1-C.sub.18alkoxy or
hydroxy-substituted C.sub.1-C.sub.18alkoxy, unsubstituted
C.sub.1-C.sub.18alkylamino, di(C.sub.1-C.sub.18alkyl)amino,
hydroxy-substituted C.sub.1-C.sub.18alkylamino or
hydroxy-substituted di(C.sub.1-C.sub.18alky- l)amino; Me is a
monovalent metal atom Z is oxygen or sulfur.
5. A composition according to claim 4, wherein R.sub.a is hydrogen
or methyl, R.sub.b is NH.sub.2, gycidyl, unsubstituted or with
hydroxy substituted C.sub.1-C.sub.4alkoxy, unsubstituted
C.sub.1-C.sub.4alkylamin- o, di(C.sub.1- C.sub.4alkyl)amino,
hydroxy-substituted C.sub.1-C.sub.4alkylamino or
hydroxy-substituted di(C.sub.1-C.sub.4alkyl)- amino;and Z is
oxygen.
6. A polymerizable composition according to claim 5, wherein the
ethylenically unsaturated monomer is methylacrylate, ethylacrylate,
butylacrylate, isobutylacrylate, tert. butylacrylate,
hydroxyethylacrylate, hydroxypropylacrylate,
dimethylaminoethylacrylate, glycidylacrylates,
methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate,
hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acryl- ate,
dimethylaminoethyl(meth)acrylate, glycidyl(meth)acrylates,
acrylonitrile, acrylamide or methacrylamide.
7. A composition according to claim 1, wherein n is 0 or 1;
R.sub.1, R.sub.2, R.sub.3 are each independently of one another
NO.sub.2, cyano, --(R.sub.9)COOR.sub.4, --CONR.sub.5R.sub.6,
--C(O)--R.sub.7, --OR.sub.8, carbamoyl,
di(C.sub.1-C.sub.18alkyl)carbamoyl, --C(.dbd.NR.sub.5)(NHR.sub-
.6); unsubstituted C.sub.1-C.sub.18alkyl,
C.sub.7-C.sub.9phenylalkyl or C.sub.3-C.sub.12cycloalkyl; or
C.sub.1-C.sub.18alkyl, C.sub.7-C.sub.9phenylalkyl or
C.sub.3-C.sub.12cycloalkyl, which are substituted by amino,
hydroxy, cyano, carboxy, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or
phenyl, which are unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, halogen, cyano, hydroxy, carboxy,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or
R.sub.2 and R.sub.3, together with the linking carbon atom, form a
C.sub.3-C.sub.12 cycloalkyl radical; R.sub.4 is,
C.sub.1-C.sub.18alkyl, phenyl, an alkali metal cation or a
tetraalkylammonium cation; R.sub.5 and R.sub.6 are hydrogen,
C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkyl which is substituted
by at least one hydroxy group or, taken together, form a
C.sub.2-C.sub.12alkylene bridge; R.sub.7 is hydrogen,
C.sub.1-C.sub.18alkyl or phenyl; R.sub.8 is C.sub.1-C.sub.18alkyl
or C.sub.2-C.sub.18alkyl which is substituted by at least one
hydroxy group; and R.sub.9 is C.sub.1-C.sub.4alkylen or a direct
bond. R.sub.10 is C.sub.4-C.sub.18alkyl bound via a tertiary C-atom
to the nitrogen atom, phenyl, C.sub.9-C.sub.11phenylalkyl or
C.sub.3-C.sub.12cycloalkyl; if n is 1 R.sub.11 is
C.sub.1-C.sub.18alkyl, C.sub.7-C.sub.9phenylalkyl or
C.sub.3-C.sub.12cycloalkyl or R.sub.10 and R.sub.11 together form a
C.sub.2-C.sub.12alkylene bridge or a C.sub.2-C.sub.12alkylene
bridge which is interrupted by at least one O or N atom, which
bridges are unsubstituted or substituted with
C.sub.1-C.sub.18alkyl; R.sub.12 is, unsubstituted
C.sub.1-C.sub.18alkyl, phenyl, C.sub.7-C.sub.9phenylalkyl or
C.sub.3-C.sub.12cycloalkyl or R.sub.11 and R.sub.12 together with
the linking carbon atom, form a C.sub.3-C.sub.12cycloalkyl
radical.
8. A composition according to claim 7, wherein n is 0 or 1;
R.sub.1, R.sub.2, R.sub.3 are each independently of one another
NO.sub.2, cyano, --(R.sub.9)COOR.sub.4, --CONR.sub.5R.sub.6,
--C(O)--R.sub.7, --OR.sub.8, carbamoyl,
di(C.sub.1-C.sub.8alkyl)carbamoyl, --C(.dbd.NR.sub.5)(NHR.sub.- 6);
unsubstituted C.sub.1-C.sub.12alkyl, C.sub.7-C.sub.9phenylalkyl or
C.sub.5-C.sub.7cycloalkyl; or C.sub.1-C.sub.8alkyl,
C.sub.7-C.sub.9phenylalkyl or C.sub.5-C.sub.7cycloalkyl or, which
are substituted by amino, hydroxy, cyano, carboxy,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or phenyl, or R.sub.2 and R.sub.3,
together with the linking carbon atom, form a C.sub.5-C.sub.7
cycloalkyl radical; R.sub.4 is C.sub.1-C.sub.8alkyl, phenyl, an
alkali metal cation or a tetraalkylammonium cation; R.sub.5 and
R.sub.6 are hydrogen, C.sub.1-C.sub.8alkyl, C.sub.2-C.sub.8alkyl
which is substituted by at least one hydroxy group or, taken
together, form a C.sub.2-C.sub.6alkylene bridge; R.sub.7 is
hydrogen, C.sub.1-C.sub.8alkyl or phenyl; R.sub.8 is
C.sub.1-C.sub.8alkyl or C.sub.2-C.sub.8alkyl which is substituted
by at least one hydroxy group; R.sub.9 is C.sub.1-C.sub.4alkylen or
a direct bond; R.sub.10 is C.sub.4-C.sub.18alkyl bound via a
tertiary C-atom to the nitrogen atom or phenyl; if n is 1 R.sub.11
is C.sub.1-C.sub.18alkyl, phenyl or C.sub.7-C.sub.9phenylalkyl or
R.sub.10 and R.sub.11 together form a C.sub.2-C.sub.12alkylene
bridge or a C.sub.2-C.sub.12alkylene bridge which is interrupted by
at least one O or N atom, which bridges are unsubstituted or
substituted with C.sub.1-C.sub.18alkyl; R.sub.12 is unsubstituted
C.sub.1-C.sub.18alkyl or phenyl.
9. A composition according to claim 8, wherein n is 0 or 1;
R.sub.1, R.sub.2, R.sub.3 are each independently of one another
NO.sub.2, cyano, --C(O)--R.sub.7, --OR.sub.8, unsubstituted
C.sub.1-C.sub.12alkyl or phenyl, which is unsubstituted or
substituted by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, cyano,
hydroxy, carboxy, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or R.sub.2 and R.sub.3, together
with the linking carbon atom, form a C.sub.5-C.sub.7 cycloalkyl
radical; R.sub.7 is, C.sub.1-C.sub.8alkyl or phenyl; R.sub.8 is
C.sub.1-C.sub.8alkyl or C.sub.2-C.sub.8alkyl which is substituted
by at least one hydroxy group and R.sub.10 is C.sub.4-C.sub.8alkyl
bound via a tertiary C-atom to the nitrogen atom, phenyl or
C.sub.9-C.sub.11phenylalk- yl; if n is 1 R.sub.11 is
C.sub.1-C.sub.12alkyl; or R.sub.10 and R.sub.11 together form a
C.sub.2-C.sub.8alkylene bridge which is unsubstituted or
substituted with C.sub.1-C.sub.4alkyl; R.sub.12 is hydrogen,
unsubstituted C.sub.1-C.sub.4alkyl or phenyl.
10. A composition according to claim 1, wherein n is 0 R.sub.1 is
cyano; R.sub.2 and R.sub.3 are each independently of one another
unsubstituted C.sub.1-C.sub.12alkyl or phenyl; or R.sub.2 and
R.sub.3, together with the linking carbon atom, form a
C.sub.5-C.sub.7 cycloalkyl radical; R.sub.10 is
C.sub.4-C.sub.12alkyl bound via a tertiary C-atom to the nitrogen
atom, C.sub.9-C.sub.11phenylalkyl or phenyl.
11. A composition according to claim 1, wherein n is 1 R.sub.1 is
cyano; R.sub.2 and R.sub.3 are each independently of one another
unsubstituted C.sub.1-C.sub.12alkyl or phenyl; or R.sub.2 and
R.sub.3, together with the linking carbon atom, form a
C.sub.5-C.sub.7 cycloalkyl radical; R.sub.10 is
C.sub.4-C.sub.12alkyl bound via a tertiary C-atom to the nitrogen
atom, C.sub.9-C.sub.11phenylalkyl or phenyl; or R.sub.10 and
R.sub.11 together form a C.sub.2-C.sub.6alkylene bridge which is
unsubstituted or substituted with C.sub.1-C.sub.4alkyl; and
R.sub.12 is C.sub.1-C.sub.4alkyl.
12. A process for preparing an oligomer, a cooligomer, a polymer or
a copolymer (block or random) by free radical polymerization of at
least one ethylenically unsaturated monomer or oligomer, which
comprises (co)polymerizing the monomer or monomers/oligomers in the
presence of an initiator compound of formula (I) according to claim
1 under reaction conditions capable of effecting scission of the
O--C bond to form two free radicals, the radical
.cndot.CR.sub.1R.sub.2R.sub.3 being capable of initiating
polymerization.
13. A process according to claim 12, wherein the scission of the
O--C bond is effected by ultrasonic treatment, heating or exposure
to actinic radiation.
14. A process according to claim 12, wherein the scission of the
O--C bond is effected by heating and takes place at a temperature
of between 50.degree. C. and 160.degree. C.
15. A process according to claim 12 for preparing a block copolymer
involving at least two stages, which comprises forming a polymer
with alkoxyamine end groups of the general structure of formula II
42wherein n, R.sub.1, R.sub.2, R.sub.3 R.sub.10 R.sub.11 and
R.sub.12 are as defined in claim 1, the polymer containing the
initiator group --CR.sub.1R.sub.2R.sub.3 and having the oxyamine
group essentially attached as terminal group, and adding a further
monomer followed by heating to form a block copolymer.
16. A process for preparing a oligomer, a cooligomer, a polymer or
a copolymer (block or random) by free radical polymerization of at
least one ethylenically unsaturated monomer or oligomer, which
comprises generating a free radical .cndot.CR.sub.1R.sub.2R.sub.3
(V) from a compound capable of eliminating a neutral molecule, or
undergoing C-C bond-scission upon thermal or photochemical
treatment, or by hydrogen abstraction from a compound
R.sub.1R.sub.2R.sub.3C--H in reaction with reactive radicals, and
reacting the free radical .cndot.CR.sub.1R.sub.2R.- sub.3 (V) with
a compound of formula R.sub.10NO or 43in a solvent which does not
interfere with the radical reaction in the presence of at least one
ethylenically unsaturated monomer or oligomer.
17. A polymer or oligomer, having at least one initiator group
--CR.sub.1R.sub.2R.sub.3 and at least one oxyamine group of formula
(IIa) 44wherein n, R.sub.1, R.sub.2, R.sub.3, R.sub.10 R.sub.11 and
R.sub.12 are as defined in claim 1, obtainable by the process
according to claim 12.
18. A compound of formula (I) 45wherein n is 0 or 1 R.sub.1,
R.sub.2, R.sub.3 are each independently of one another hydrogen,
halogen, NO.sub.2, cyano, --CONR.sub.5R.sub.6,
--(R.sub.9)COOR.sub.4, --C(O)--R.sub.7, --OR.sub.8, --SR.sub.8,
--NHR.sub.8, --N(R.sub.8).sub.2, carbamoyl,
di(C.sub.1-C.sub.18alkyl)carbamoyl, --C(.dbd.NR.sub.5)(NHR.sub-
.6); unsubstituted C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkenyl,
C.sub.2-C.sub.18alkynyl, C.sub.7-C.sub.9phenylalkyl,
C.sub.3-C.sub.12cycloalkyl or C.sub.3-C.sub.12cycloalkyl containing
at least one nitrogen or oxygen atom; or C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18 alkynyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom, which are substituted by NO.sub.2, halogen, amino,
hydroxy, cyano, carboxy, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or phenyl, naphthyl, which are
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio, halogen, cyano,
hydroxy, carboxy, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or R.sub.2 and R.sub.3, together
with the linking carbon atom, form a C.sub.3-C.sub.12 cycloalkyl
radical, a (C.sub.4-C.sub.12 cycloalkanon)-yl radical or a
C.sub.3-C.sub.12cycloalkyl radical containing at least one O atom
46and/or a NR.sub.8 group; or if n is1 R.sub.4 is hydrogen,
C.sub.1-C.sub.18alkyl, phenyl, an alkali metal cation or a
tetraalkylammonium cation; R.sub.5 and R.sub.6 are hydrogen,
C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkyl which is substituted
by at least one hydroxy group or, taken together, form a
C.sub.2-C.sub.12alkylene bridge or a C.sub.2-C.sub.12-alkylene
bridge interrupted by at least one O or/and NR.sub.8 atom; R.sub.7
is hydrogen, C.sub.1-C.sub.18alkyl or phenyl; R.sub.8 is hydrogen,
C.sub.1-C.sub.18alkyl or C.sub.2-C.sub.18alkyl which is substituted
by at least one hydroxy group; R.sub.9 is C.sub.1-C.sub.12alkylen
or a direct bond; R.sub.10 is C.sub.4-C.sub.18alkyl bound via a
tertiary C-atom to the nitrogen atom, C.sub.9-C.sub.11phenylalkyl,
C.sub.3-C.sub.12cycloalky- l or C.sub.3-C.sub.12cycloalkyl
containing at least one nitrogen or oxygen atom; or
C.sub.4-C.sub.18alkyl bound via a tertiary C-atom to the nitrogen
atom, C.sub.9-C.sub.11phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom, which are substituted by NO.sub.2, halogen, amino,
hydroxy, cyano, carboxy, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or phenyl, naphthyl, which are
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio, halogen, cyano,
hydroxy, carboxy, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or a polycyclic cycloaliphatic ring
system or a polycyclic cycloaliphatic ring system with at least one
di- or trivalent nitrogen atom; if n is 1 R.sub.11 is
C.sub.1-C.sub.18alkyl, C.sub.7-C.sub.9phenylalkyl,
C.sub.3-C.sub.12cycloalkyl or C.sub.3-C.sub.12cycloalkyl containing
at least one nitrogen or oxygen atom; or C.sub.1-C.sub.18alkyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom, which are substituted by NO.sub.2, halogen, amino,
hydroxy, cyano, carboxy, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or phenyl, naphthyl, which are
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio, halogen, cyano,
hydroxy, carboxy, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or a polycyclic cycloaliphatic ring
system or a polycyclic cycloaliphatic ring system with at least one
di- or trivalent nitrogen atom; or R.sub.10 and R.sub.11 together
form a C.sub.2-C.sub.12alkylene bridge, a
C.sub.3-C.sub.12alkylen-on bridge or a C.sub.2-C.sub.12alkylene
bridge which is interrupted by at least one O or N atom, which
bridges are unsubstituted or substituted with
C.sub.1-C.sub.18alkyl, hydroxy(C.sub.1-C.sub.4)alkyl, phenyl,
C.sub.7-C.sub.9phenylalkyl, NO.sub.2, halogen, amino, hydroxy,
cyano, carboxy, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino, or
R.sub.12 is hydrogen, --(R.sub.9)COOR.sub.4, cyano, --OR.sub.8,
--SR.sub.8, --NHR.sub.8, --N(R.sub.8).sub.2, --NH--C(O)--R.sub.8,
unsubstituted C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkenyl,
C.sub.2-C.sub.18alkynyl, C.sub.7-C.sub.9phenylalkyl,
C.sub.3-C.sub.12cycloalkyl or C.sub.3-C.sub.12cycloalkyl containing
at least one nitrogen or oxygen atom; or C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18 alkynyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom, which are substituted by NO.sub.2, halogen, amino,
hydroxy, cyano, carboxy, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or phenyl, naphthyl, which are
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio, halogen, cyano,
hydroxy, carboxy, C.sub.1-C.sub.4alkylamino,
di(C.sub.1-C.sub.4alkyl)amino; or R.sub.11 and R.sub.12 together
with the linking carbon atom, form a C.sub.3-C.sub.12cycloalkyl
radical; with the proviso that if n is 0 R.sub.10 is different from
the group --CR.sub.1R.sub.2R.sub.3, and if R.sub.1 is CN and
R.sub.2 and R.sub.3 are methyl, R.sub.10 is not phenyl, phenyl
substituted by methyl, 2,4,6-trimethyl, chlor, fluor,
(3-methyl,4-fluor), (3-fluor, 4-methyl), (4-fluor, 2-methyl),
(4-fluor, 2-methoxy), (2-fluor, 3,5-methyl), 2,5-di-tert.butyl,
nitro, 3,5-dinitro or 2 (--O--C(CH.sub.3).sub.2CN) 4-nitro; and if
n is 1, R.sub.12 is hydrogen, R.sub.10 phenyl or benzyl and
R.sub.11 phenyl, R.sub.1, R.sub.2 and R.sub.3 are not a group
--C(CH.sub.3).sub.2CN, --C(CH.sub.3).sub.2COOCH.sub.3, benzyl,
methylbenzyl, dimethylbenzyl, 47and 48the compound according to
formula I is not
19. A compound according to claim 18, wherein n is 0 or 1; R.sub.1,
R.sub.2, R.sub.3 are each independently of one another NO.sub.2,
cyano, --C(O)--R.sub.7, --OR.sub.8, unsubstituted
C.sub.1-C.sub.12alkyl or phenyl, which is unsubstituted or
substituted by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, cyano,
hydroxy, carboxy, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or R.sub.2 and R.sub.3, together
with the linking carbon atom, form a C.sub.5-C.sub.7 cycloalkyl
radical; R.sub.7 is, C.sub.1-C.sub.8alkyl or phenyl; R.sub.8 is
C.sub.1-C.sub.8alkyl or C.sub.2-C.sub.8alkyl which is substituted
by at least one hydroxy group and R.sub.10 is C.sub.4-C.sub.18alkyl
bound via a tertiary C-atom to the nitrogen atom, phenyl or
C.sub.9-C.sub.11phenylalk- yl; if n is 1 R.sub.11 is
C.sub.1-C.sub.18alkyl, C.sub.7-C.sub.9phenylalky- l or
C.sub.3-C.sub.12cycloalkyl or R.sub.10 and R.sub.11 together form a
C.sub.2-C.sub.6alkylene bridge which is unsubstituted or
substituted with C.sub.1-C.sub.4alkyl; R.sub.12 is, unsubstituted
C.sub.1-C.sub.4alkyl or phenyl.
20. A compound according to claim 18, wherein n is 0 R.sub.1 is
cyano; R.sub.2 and R.sub.3 are each independently of one another
unsubstituted C.sub.1-C.sub.12alkyl or phenyl; or R.sub.2 and
R.sub.3, together with the linking carbon atom, form a
C.sub.5-C.sub.7 cycloalkyl radical; R.sub.10 is
C.sub.4-C.sub.12alkyl bound via a tertiary C-atom to the nitrogen
atom, C.sub.9-C.sub.11,phenylalkyl or phenyl.
21. A compound according to claim 18, wherein n is 1 R.sub.1 is
cyano; R.sub.2 and R.sub.3 are each independently of one another
unsubstituted C.sub.1-C.sub.12alkyl or phenyl; or R.sub.2 and
R.sub.3, together with the linking carbon atom, form a
C.sub.5-C.sub.7cycloalkyl radical; R.sub.10 is
C.sub.4-C.sub.12alkyl bound via a tertiary C-atom to the nitrogen
atom, C.sub.9-C.sub.11phenylalkyl or phenyl; or R.sub.10 and
R.sub.11 together form a C.sub.2-C.sub.6alkylene bridge which is
unsubstituted or substituted with C.sub.1-C.sub.4alkyl; and
R.sub.12 is C.sub.1-C.sub.4alkyl.
22. A compound of formula (IV) 49wherein n is 0 or 1 R.sub.1,
R.sub.2, R.sub.3 are each independently of one another hydrogen,
halogen, NO.sub.2, cyano, --CONR.sub.5R.sub.6,
--(R.sub.9)COOR.sub.4, --C(O)--R.sub.7, --OR.sub.8, --SR.sub.8,
--NHR.sub.8, --N(R.sub.8).sub.2, carbamoyl,
di(C.sub.1-C.sub.18alkyl)carbamoyl, --C(.dbd.NR.sub.5)(NHR.sub-
.6); unsubstituted C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkenyl,
C.sub.2-C.sub.18alkynyl, C.sub.7-C.sub.9phenylalkyl,
C.sub.3-C.sub.12cycloalkyl or C.sub.3-C.sub.12cycloalkyl containing
at least one nitrogen or oxygen atom; or C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18 alkynyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom, which are substituted by NO.sub.2, halogen, amino,
hydroxy, cyano, carboxy, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or phenyl, naphthyl, which are
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio, halogen, cyano,
hydroxy, carboxy, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or R.sub.2 and R.sub.3, together
with the linking carbon atom, form a C.sub.3-C.sub.12 cycloalkyl
radical, a (C.sub.4-C.sub.12 cycloalkanon)-yl radical or a
C.sub.3-C.sub.12cycloalkyl radical containing at least one O atom
and/or a NR.sub.8 group; or if n is 1 50R.sub.4 is hydrogen,
C.sub.1-C.sub.18alkyl, phenyl, an alkali metal cation or a
tetraalkylammonium cation; R.sub.5 and R.sub.6 are hydrogen,
C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkyl which is substituted
by at least one hydroxy group or, taken together, form a
C.sub.2-C.sub.12alkylene bridge or a C.sub.2-C.sub.12-alkylene
bridge interrupted by at least one O or/and NR.sub.8 atom; R.sub.7
is hydrogen, C.sub.1-C.sub.18alkyl or phenyl; R.sub.8 is hydrogen,
C.sub.1-C.sub.18alkyl or C.sub.2-C.sub.18alkyl which is substituted
by at least one hydroxy group; R.sub.9 is C.sub.1-C.sub.12alkylen
or a direct bond; R.sub.10 is C.sub.4-C.sub.12alkyl bound via a
tertiary C-atom to the nitrogen atom, C.sub.9-C.sub.11phenylalkyl,
C.sub.3-C.sub.12cycloalky- l or C.sub.3-C.sub.12cycloalkyl
containing at least one nitrogen or oxygen atom; or
C.sub.4-C.sub.18alkyl bound via a tertiary C-atom to the nitrogen
atom, C.sub.9-C.sub.11phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom, which are substituted by NO.sub.2, halogen, amino,
hydroxy, cyano, carboxy, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or phenyl, naphthyl, which are
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio, halogen, cyano,
hydroxy, carboxy, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or a polycyclic cycloaliphatic ring
system or a polycyclic cycloaliphatic ring system with at least one
di- or trivalent nitrogen atom; if n is 1 R.sub.11 is
C.sub.1-C.sub.18alkyl, C.sub.7-C.sub.9phenylalkyl,
C.sub.3-C.sub.12cycloalkyl or C.sub.3-C.sub.12cycloalkyl containing
at least one nitrogen or oxygen atom; or C.sub.1-C.sub.18alkyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom, which are substituted by NO.sub.2, halogen, amino,
hydroxy, cyano, carboxy, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or phenyl, naphthyl,, which are
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio, halogen, cyano,
hydroxy, carboxy, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or a polycyclic cycloaliphatic ring
system or a polycyclic cycloaliphatic ring system with at least one
di- or trivalent nitrogen atom; or R.sub.10 and R.sub.11 together
form a C.sub.2-C.sub.12alkylene bridge, a C.sub.3-C.sub.12
alkylen-on bridge or a C.sub.2-C.sub.12alkylene bridge which is
interrupted by at least one O or N atom, which bridges are
unsubstituted or substituted with C.sub.1-C.sub.18alkyl,
hydroxy(C.sub.1-C.sub.4)alkyl, phenyl, C.sub.7-C.sub.9phenylalkyl,
NO.sub.2, halogen, amino, hydroxy, cyano, carboxy,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino;
R.sub.12 is hydrogen, --(R.sub.9)COOR.sub.4, cyano, --OR.sub.8,
--SR.sub.8, --NHR.sub.8, --N(R.sub.8).sub.2, --NH--C(O)--R.sub.8,
unsubstituted C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkenyl,
C.sub.2-C.sub.18alkynyl, C.sub.7-C.sub.9phenylalkyl,
C.sub.3-C.sub.12cycloalkyl or C.sub.3-C.sub.12cycloalkyl containing
at least one nitrogen or oxygen atom; or C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18 alkynyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom, which are substituted by NO.sub.2, halogen, amino,
hydroxy, cyano, carboxy, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or phenyl, naphthyl, which are
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio, halogen, cyano,
hydroxy, carboxy, C.sub.1-C.sub.4alkylamino,
di(C.sub.1-C.sub.4alkyl)amino; or R.sub.11 and R.sub.12 together
with the linking carbon atom, form a C.sub.3-C.sub.12 cycloalkyl
radical; with the proviso that if n is 0 R.sub.10 is different from
the group --CR.sub.1R.sub.2R.sub.3, and if R.sub.1 is CN and
R.sub.2 and R.sub.3 are methyl, R.sub.10 is not phenyl, phenyl
substituted by methyl, 2,4,6-trimethyl, chlor, fluor,
(3-methyl,4-fluor), (3-fluor, 4-methyl), (4-fluor, 2-methyl),
(4-fluor, 2-methoxy), (2-fluor, 3,5-methyl), 2,5-di-tert.butyl,
nitro, 3,5-dinitro or 2 (--O--C(CH.sub.3).sub.2CN) 4-nitro; and if
n is 1, R.sub.12 is hydrogen, R.sub.10 phenyl or benzyl and
R.sub.11 phenyl, R.sub.1, R.sub.2 and R.sub.3 are not a group
--C(CH.sub.3).sub.2CN, --C(CH.sub.3).sub.2COOCH.sub.3, benzyl,
methylbenzyl, dimethylbenzyl, 51and the compound according to
formula IV is not 52
23. A process for preparing a compound of formula (I) according to
claim 1 53by generating a free radical
.cndot.CR.sub.1R.sub.2R.sub.3 (V) from a compound capable of
eliminating a neutral molecule, or undergoing C-C bond-scission
upon thermal or photochemical treatment, or by hydrogen abstraction
from a compound R.sub.1R.sub.2R.sub.3C--H in reaction with reactive
radicals, and reacting the free radical .cndot.CR.sub.1R.sub.2R.-
sub.3 (V) with a compound of formula R.sub.10NO or 54in a solvent
which does not interfere with the radical reaction.
24. A process according to claim 23 wherein the free radical
.cndot.CR.sub.1R.sub.2R.sub.3 is prepared by heating or irradiation
of a compound of formula IIIa, IIIb or IIIc 55
25. A process according to claim 23, wherein the radical
.cndot.CR.sub.1R.sub.2R.sub.3 is prepared by heating at a
temperature from 40 to 150.degree. C.
26. A process according to claim 23, wherein the free radical
source is 2,2'-azobisisobutyronitrile,
2,2'-azobis(2-methylbutyronitrile),
2,2'-azobis(2,4-dimethylvaleronitrile),
2,2'-azobis-(4-methoxy-2,4-dimeth- ylvaleronitrile),
1,1'-azobis(1-cyclohexanecarbonitrile),
4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis(isobutyramide),
dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile,
dimethyl-2,2'-azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile,
2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane),
2,2'-azobis(N,N'-dimethyleneisobutyramidine), free base or
hydrochloride, 2,2'-azobis(2-amidinopropane), free base or
hydrochloride,
2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide}
or
2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamid-
e.
27. Use of a compound of formula I according to claim 1 for
polymerizing ethylenically unsaturated monomers.
28. A polymerizable composition, comprising a) at least one
ethylenically unsaturated monomer or oligomer; b) a compound of
formula (IV) and c) a radical initiator according to claim 23
capable of generating a free radical of formula (V) 56wherein n,
R.sub.1, R.sub.2, R.sub.3, R.sub.10, R.sub.11 and R.sub.12 are as
defined in claim 1.
Description
[0001] The present invention relates to a polymerizable composition
comprising a) at least one ethylenically unsaturated monomer and b)
a nitroxide initiator compound. Further aspects of the present
invention are a process for polymerizing ethylenically unsaturated
monomers, novel initiator compounds and their use for
polymerization, and also the polymer or copolymer produced by this
process.
[0002] More specifically, in one of its aspects the present
invention relates to polymerizable compositions and polymerization
processes which provide polymeric resin products having low
polydispersity , which polymerization processes proceed with
enhanced monomer to polymer conversion efficiencies. In particular,
this invention relates to stable free radical-mediated
polymerization processes which provide homopolymers, random
copolymers, block copolymers, multiblock copolymers, graft
copolymers and the like, at enhanced rates of polymerization and
enhanced monomer to polymer conversions.
[0003] Polymers or copolymers prepared by free radical
polymerization processes inherently have broad molecular weight
distributions or polydispersities which are generally higher than
about four. One reason for this is that most of the free radical
initiators have half lives that are relatively long, ranging from
several minutes to many hours, and thus the polymeric chains are
not all initiated at the same time and the initiators provide
growing chains of various lengths at any time during the
polymerization process. Another reason is that the propagating
chains in a free radical process can react with each other in
processes known as combination and disproportionation, both of
which are irreversibly chain-terminating reaction processes. In
doing so, chains of varying lengths are terminated at different
times during the reaction process, resulting in resins consisting
of polymeric chains which vary widely in length from very small to
very large and which thus have broad polydispersities. If a free
radical polymerization process is to be used for producing narrow
molecular weight distributions, then all polymer chains must be
initiated at about the same time and termination of the growing
polymer-chains by combination or disproportionation processes must
be avoided.
[0004] Conventional radical polymerization reaction processes pose
various significant problems, such as difficulties in predicting or
controlling the molecular weight, the polydispersity and the
modality of the polymers produced. These prior art polymerization
processes produce polymers having broad polydispersities and in
some instances, low polymerization rates. Furthermore, free radical
polymerization processes in bulk of the prior art are difficult to
control because the polymerization reaction is strongly exothermic
and an efficient heat removal in the highly viscous polymer is
mostly impossible. The exothermic nature of the prior art free
radical polymerization processes often severely restricts the
concentration of reactants or the reactor size upon scale-up.
[0005] Due to the above mentioned uncontrollable polymerization
reactions, gel formation in conventional free radical
polymerization processes are also possible and cause broad
molecular weight distributions and/or difficulties during
filtering, drying and manipulating the product resin.
[0006] U.S. Pat. No. 4 581 429 to Solomon et al., issued Apr. 8,
1986, discloses a free radical polymerization process which
controls the growth of polymer chains to produce short chain or
oligomeric homopolymers and copolymers, including block and graft
copolymers. The process employs an initiator having the formula (in
part) R'R"N--O--X, where X is a free radical species capable of
polymerizing unsaturated monomers. The reactions typically have low
conversion rates. Specifically mentioned radical R'R"N--O.cndot.
groups are derived from 1,1,3,3 tetraethylisoindoline, 1,1,3,3
tetrapropylisoindoline, 2,2,6,6 tetramethylpiperidine, 2,2,5,5
tetramethylpyrrolidine or di-t-butylamine.
[0007] EP-A-735 052 discloses a method of preparing thermoplastic
polymers of narrow polydispersities by free radical-initated
polymerization, which comprises adding a free radical initiator and
a stable free radical agent to the monomer compound.
[0008] This method has the disadvantage that uncontrollable
recombinations of initiator radicals occur immidiately after their
formation, thus producing variable ratios between initiator
radicals and stable free radicals. Consequently there is not enough
control about the polymerization process.
[0009] There is therefore still a need for polymerization processes
for the preparation of narrow polydispersity polymeric resins with
defined molecular weights using the economical free radical
polymerization techniques. These polymerization processes will also
control the physical properties of the polymers such as viscosity,
hardness, gel content, processability, clarity, high gloss,
durability, and the like.
[0010] The polymerization processes and resin products of the
present invention are useful in many applications, including a
variety of specialty applications, such as for the preparation of
block copolymers which are useful as compatibilizing agents for
polymer blends, or dispersing agents for coating systems or for the
preparation of narrow molecular weight resins or oligomers for use
in coating technologies and thermoplastic films or as toner resins
and liquid immersion development ink resins or ink additives used
for electrophotographic imaging processes.
[0011] Surprisingly, it has now been found that it is possible to
overcome the afore mentioned shortcomings of the prior art by
providing a polymerizable composition containing specific initiator
compounds. The majority of these compounds are novel and they are
also an object of the present invention. Polymerization of the
composition results in a polymer or copolymer of narrow
polydispersity and a high monomer to polymer conversion even at
relatively low temperatures and at short reaction times, making the
polymerization process particularly suitable for industrial
applications. The resulting copolymers are of high purity and in
many cases colourless, therefore not requiring any further
purification.
[0012] One object of the present invention is to provide a
polymerizable composition, comprising
[0013] a) at least one ethylenically unsaturated monomer or
oligomer, and
[0014] b) an initiator compound of formula (I) 4
[0015] wherein n is 0 or 1
[0016] R.sub.1, R.sub.2, R.sub.3 are each independently of one
another hydrogen, halogen, NO.sub.2, cyano, --CONR.sub.5R.sub.6,
--(R.sub.9)COOR.sub.4, --C(O)--R.sub.7, --OR.sub.8, --SR.sub.8,
--NHR.sub.8, --N(R.sub.8).sub.2, carbamoyl,
di(C.sub.1-C.sub.18alkyl)carb- amoyl,
--C(.dbd.NR.sub.5)(NHR.sub.6);
[0017] unsubstituted C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom; or C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkenyl,
C.sub.2-C.sub.18 alkynyl, C.sub.7-C.sub.9phenylalkyl,
C.sub.3-C.sub.12cycloalkyl or C.sub.3-C.sub.12cycloalkyl containing
at least one nitrogen or oxygen atom, which are substituted by
NO.sub.2, halogen, amino, hydroxy, cyano, carboxy,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or
[0018] phenyl, naphthyl, which are unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, halogen, cyano, hydroxy, carboxy,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or
R.sub.2 and R.sub.3, together with the linking carbon atom, form a
C.sub.3-C.sub.12 cycloalkyl radical, a (C.sub.4-C.sub.12
cycloalkanon)-yl radical or a C.sub.3-C.sub.12cycloalky- l radical
containing at least one O atom and/or a NR.sub.8 group; or if n is
1 5
[0019] R.sub.4 is hydrogen, C.sub.1-C.sub.18alkyl, phenyl, an
alkali metal cation or a tetraalkylammonium cation; R.sub.5 and
R.sub.6 are hydrogen, C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkyl
which is substituted by at least one hydroxy group or, taken
together, form a C.sub.2-C.sub.12alkylene bridge or a
C.sub.2-C.sub.12-alkylene bridge interrupted by at least one O
or/and NR.sub.8 atom;
[0020] R.sub.7 is hydrogen, C.sub.1-C.sub.18alkyl or phenyl;
[0021] R.sub.8 is hydrogen, C.sub.1-C.sub.18alkyl or
C.sub.2-C.sub.18alkyl which is substituted by at least one hydroxy
group;
[0022] R.sub.9 is C.sub.4-C.sub.12alkylen or a direct bond;
[0023] R.sub.10 is C.sub.4-C.sub.18alkyl bound via a tertiary
C-atom to the nitrogen atom, C.sub.9-C.sub.11phenylalkyl,
C.sub.3-C.sub.12cycloalky- l or C.sub.3-C.sub.12cycloalkyl
containing at least one nitrogen or oxygen atom; or
C.sub.4-C.sub.18alkyl bound via a tertiary C-atom to the nitrogen
atom, C.sub.9-C.sub.11phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom, which are substituted by NO.sub.2, halogen, amino,
hydroxy, cyano, carboxy, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or
[0024] phenyl, naphthyl, which are unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, halogen, cyano, hydroxy, carboxy,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; if n is
1
[0025] R.sub.11 is C.sub.1-C.sub.18alkyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom; or
[0026] C.sub.1-C.sub.18alkyl, C.sub.7-C.sub.9phenylalkyl,
C.sub.3-C.sub.12cycloalkyl or C.sub.3-C.sub.12cycloalkyl containing
at least one nitrogen or oxygen atom, which are substituted by
NO.sub.2, halogen, amino, hydroxy, cyano, carboxy,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or
phenyl, naphthyl, which are unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, halogen, cyano, hydroxy, carboxy,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or a
polycyclic cycloaliphatic ring system or a polycyclic
cycloaliphatic ring system with at least one di- or trivalent
nitrogen atom; or
[0027] R.sub.10 and R.sub.11 together form a
C.sub.2-C.sub.12alkylene bridge, a C.sub.3-C.sub.12alkylen-on
bridge or a C.sub.2-C.sub.12alkylene bridge which is interrupted by
at least one O or N atom, which bridges are unsubstituted or
substituted with C.sub.1-C.sub.18alkyl,
hydroxy(C.sub.1-C.sub.4)alkyl, phenyl, C.sub.7-C.sub.9phenylalkyl,
NO.sub.2, halogen, amino, hydroxy, cyano, carboxy,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino,
[0028] R.sub.12 is hydrogen, --(R.sub.9)COOR.sub.4, cyano,
--OR.sub.8, --SR.sub.8, --NHR.sub.8, --N(R.sub.8).sub.2,
--NH--C(O)--R.sub.8, unsubstituted C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom; or C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkenyl,
C.sub.2-C.sub.18 alkynyl, C.sub.7-C.sub.9phenylalkyl,
C.sub.3-C.sub.12cycloalkyl or C.sub.3-C.sub.12cycloalkyl containing
at least one nitrogen or oxygen atom, which are substituted by
NO.sub.2, halogen, amino, hydroxy, cyano, carboxy,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or
[0029] phenyl, naphthyl, which are unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, halogen, cyano, hydroxy, carboxy,
C.sub.1-C.sub.4alkylamino, di(C.sub.1-C.sub.4alkyl)amino; or
R.sub.11 and R.sub.12 together with the linking carbon atom form a
C.sub.3-C.sub.12cycloalkyl radical; with the proviso that
bis-(2-cyano-2-propyl)-N-phenylhydroxylamine is excluded and if n=0
R.sub.10 is different from the group --CR.sub.1R.sub.2R.sub.3.
[0030] The initiator compound of formula (I) is preferably present
in an amount of 0.01 mol-% to 30 mol-%, more preferably in an
amount of 0.1 mol-% to 10 mol-% and most preferably in an amount of
0.1 to 5 mol-%, based on the monomer, oligomer or monomer/oligomer
mixture used.
[0031] Preferrably compounds of formula (I) do not contain the
structural element 2,2,6,6 tetra(C.sub.1-C.sub.4alkyl)piperidine,
2,2,5,5 tetra(C.sub.1-C.sub.4alkyl)pyrrolidin or 1,1,3,3
tetra(C.sub.1-C.sub.4alk- yl)isoindoline
[0032] Halogen is fluoro, chloro, bromo or iodo.
[0033] The alkyl radicals in the various substituents may be linear
or branched. Examples of alkyl containing 1 to 18 carbon atoms are
methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl,
t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl,
t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,
hexadecyl and octadecyl.
[0034] The alkenyl radicals in the various substituents may be
linear or branched. Examples of C.sub.2-C.sub.18alkenyl are vinyl,
allyl, 2-methylallyl, butenyl, hexenyl, undecenyl and octadecenyl.
Preferred alkenyls are those, wherein the carbon atom in the
1-position is saturated and where the double bond is not activated
by substituents like O, C.dbd.O, and the like. Examples of
C.sub.2-C.sub.18alkynyl are ethynyl, 2-butynyl, 3-hexynyl,
5-undecynyl, 6-octadecynyl. The alkynyl radicals may be linear or
branched.
[0035] C.sub.7-C.sub.9phenylalkyl is for example benzyl,
phenylpropyl, .alpha.,.alpha.-dimethylbenzyl or
.alpha.-methylbenzyl.
[0036] C.sub.9-C.sub.11phenylalkyl is for example
.alpha.,.alpha.-dimethyl- benzyl, .alpha.,.alpha.-metylethylbenzyl
or .alpha.,.alpha.-diethylbenzyl.
[0037] C.sub.3-C.sub.12cycloalkyl which is unsubstituted or
substituted by 1, 2 or 3 C.sub.1-C.sub.4alkyl is typically
cyclopropyl, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl,
cyclohexyl, methylcyclohexyl.
[0038] Alkyl substituted by --OH is typically 2-hydroxyethyl,
2-hydroxypropyl or 2-hydroxybutyl.
[0039] C.sub.1-C.sub.18Alkyl substituted by C.sub.1-C.sub.18alkoxy,
preferably by C.sub.1-C.sub.4alkoxy, in particular by methoxy or
ethoxy, is typically 2-methoxyethyl, 2-ethoxyethyl,
3-methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl, 3-octoxypropyl and
4-methoxybutyl.
[0040] C.sub.1-C.sub.18Alkyl substituted by
di(C.sub.1-C.sub.4alkyl)amino is preferably e.g. dimethylamino,
diethylamino, 2-dimethylaminoethyl, 2-diethylaminoethyl,
3-dimethylaminopropyl, 3-diethylaminopropyl, 3-dibutylaminopropyl
and 4-diethylaminobutyl.
[0041] C.sub.1-C.sub.18AIkyl substituted by
C.sub.1-C.sub.4alkylamino is preferably e.g. methylamino,
ethylamino, 2-methylaminoethyl, 2-ethylaminoethyl,
3-methylaminopropyl, 3-ethylaminopropyl, 3-butylaminopropyl and
4-ethylaminobutyl.
[0042] C.sub.1-C.sub.8AIkoxy and, preferably C.sub.1-C.sub.4alkoxy,
are typically methoxy, ethoxy, propoxy, isopropoxy, butoxy,
isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy or octoxy.
[0043] C.sub.1-C.sub.4Alkylthio is typically thiomethyl, thioethyl,
thiopropyl, thioisopropyl, thiobutyl and thioisobutyl.
[0044] C.sub.3-C.sub.12cycloalkyl interrupted by at least on
nitrogen or oxygen atom is typically oxiran, 1,4-dioxane,
tetrahydrofuran, .gamma.-butyrolactone, .epsilon.-caprolactam,
oxirane, aziridine, diaziridine, pyrrole, pyrrolidine, thiophen,
furan, pyrazole, imidazole, oxazole, oxazolidine, thiazole, pyran,
thiopyran, piperidine or morpholine.
[0045] Examples of C.sub.2-C.sub.12alkylene bridges, preferably of
C.sub.2-C.sub.6alkylene bridges, are ethylene, propylene, butylene,
pentylene, hexylene.
[0046] C.sub.2-C.sub.12alkylene bridges interrupted by at least one
N or O atom are, for example, --CH.sub.2--O--CH.sub.2--CH.sub.2,
--CH.sub.2--O--CH.sub.2--CH.sub.2,
--CH.sub.2--O--CH.sub.2--CH.sub.2--CH.- sub.2--CH.sub.2--,
--CH.sub.2--O--CH.sub.2--CH.sub.2--O--CH.sub.2--,
--CH.sub.2--NH--CH.sub.2--CH.sub.2,
--CH.sub.2--NH--CH.sub.2--CH.sub.2--C- H.sub.2,
--CH.sub.2--NH--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2--,
--CH.sub.2--NH--CH.sub.2--CH.sub.2--NH--CH.sub.2-- or
--CH.sub.2--NH--CH.sub.2--CH.sub.2--O--CH2--.
[0047] Examples for C.sub.4-C.sub.12cycloalkanone-yl are
cyclopentanone-yl, cyclohexanone-yl or cycloheptanone-yl.
[0048] Phenyl substituted by 1, 2 or 3 C.sub.1-C.sub.4alkyl or
C.sub.1-C.sub.4alkoxy is typically methylphenyl, dimethylphenyl,
trimethylphenyl, t-butylphenyl, di-t-butylphenyl,
3,5-di-t-butyl-4-methyl- phenyl, methoxyphenyl, ethoxyphenyl and
butoxyphenyl.
[0049] Examples of polycyclic cycloaliphatic ring systems are
adamantane, cubane, twistane, norbornane, bycyclo[2.2.2]octane or
bycyclo[3.2.1]octane.
[0050] An example of a polycyclic heterocycloaliphatic ring system
is hexamethylentetramine (urotropine).
[0051] The C-atom to which the substituents R.sub.1, R.sub.2 and
R.sub.3 are bound is preferably a secondary or tertiary C-atom more
preferably it is a tertiary C-atom.
[0052] Examples for C.sub.4-C.sub.18alkyl bound via a tertiary
C-atom to the nitrogen atom are the following groups: 6
[0053] The monomers suitable for use in the present invention may
be water-soluble or water-insoluble. Water soluble monomers contain
typically a carboxylic acid group or a salt of a carboxylic acid
group. Water insoluble monomers are typically free of acid and
phenolic groups.
[0054] Typical monoethylenically unsaturated monomers free of
carboxylic acid which are suitable for this invention include the
alkyl esters of acrylic or methacrylic acids such as methyl
acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate,
ethyl methacrylate, butyl methacrylate and isobutyl methacrylate;
the hydroxyalkyl esters of acrylic or methacrylic acids, such as
hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl
methacrylate, and hydroxypropyl methacrylate; acrylamide,
methacrylamide, N-tertiary butylacrylamide, N-methylacrylamide,
N,N-dimethylacrylamide; acrylonitrile, methacrylonitrile, allyl
alcohol, dimethylaminoethyl acrylate, dimethylaminoethyl
methacrylate, phosphoethyl methacrylate, N-vinylpyrrolidone,
N-vinylformamide, N-vinylimidazole, vinyl acetate, conjugated
dienes such as butadiene or isoprene, styrene, styrenesulfonic acid
salts, vinylsulfonic or 2-acrylamido-2-methylpropane-sulfonic acid
salts and acryloyl chloride.
[0055] The polymerizable composition of the present invention may
additionally comprise a solvent selected from the group consisting
of water, alcohols, esters, ethers, ketones, amides, sulfoxides,
hydrocarbons and halogenated hydrocarbons.
[0056] Preferred ethylenically unsaturated monomers or oligomers
are selected from the group consisting of styrene, substituted
styrene, conjugated dienes, acrolein, vinyl acetate, (alkyl)acrylic
acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylic esters or
(alkyl)acrylamides.
[0057] Particularly preferred ethylenically unsaturated monomers
are styrene, .alpha. methyl styrene, .rho.-methyl styrene or a
compound of formula CH.sub.2.dbd.C(R.sub.a)--(C.dbd.Z)--R.sub.b,
wherein R.sub.a is hydrogen or C.sub.1-C.sub.4alkyl, R.sub.b is
NH.sub.2, O(Me), glycidyl, unsubstituted C.sub.1-C.sub.18alkoxy or
hydroxy-substituted C.sub.1-C.sub.18alkoxy, unsubstituted
C.sub.1-C.sub.18alkylamino, di(C.sub.1-C.sub.18alkyl)amino,
hydroxy-substituted C.sub.1-C.sub.18alkylamino or
hydroxy-substituted di(C.sub.1-C.sub.18alky- l)amino;
[0058] Me is a monvalent metal atom and
[0059] Z is oxygen or sulfur.
[0060] Typical metal atoms are Na, K or Li.
[0061] Examples and preferences for alkyl, alkoxy, alkylamino,
dialkylamino and hydroxy-substituted alkoxy are afore
mentioned.
[0062] In a particular preferred composition R.sub.a is hydrogen or
methyl, R.sub.b is NH.sub.2, glycidyl, unsubstituted or with
hydroxy substituted C.sub.1-C.sub.4alkoxy, unsubstituted
C.sub.1-C.sub.4alkylamin- o, di(C.sub.1-C.sub.4alkyl)amino,
hydroxy-substituted C.sub.1-C.sub.4alkylamino or
hydroxy-substituted di(C.sub.1-C.sub.4alkyl)- amino;and
[0063] Z is oxygen.
[0064] Most preferred is a polymerizable composition, wherein the
ethylenically unsaturated monomer is methylacrylate, ethylacrylate,
butylacrylate, isobutylacrylate, tert. butylacrylate,
hydroxyethylacrylate, hydroxypropylacrylate,
dimethylaminoethylacrylate, glycidylacrylates,
methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate,
hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acryl- ate,
dimethylaminoethyl(meth)acrylate, glycidyl(meth)acrylates,
acrylonitrile, acrylamide or methacrylamide.
[0065] Examples of comonomers suitable for use in the present
invention are C.sub.3-C.sub.6ethylenically unsaturated
monocarboxylic acids as well as the alkali metal salts and ammonium
salts thereof. The C.sub.3-C.sub.6ethylenically unsaturated
monocarboxylic acids include acrylic acid, methacrylic acid,
crotonic acid, vinylacetic acid and acryloxypropionic acid. Acrylic
acid and methacrylic acid are the preferred monoethylenically
unsaturated monocarboxylic acid monomers.
[0066] Examples for C.sub.8-C.sub.16 ethylenically unsaturated
phenolics, which may also be used as comonomers include 4-hydroxy
styrene, 4-hydroxy, .alpha.-methyl styrene, and 2,6-ditert. butyl,
4-vinyl phenol.
[0067] Another class of carboxylic acid monomers suitable for use
as comonomers in this invention are C.sub.4-C.sub.6-ethylenically
unsaturated dicarboxylic acids and the alkali metal and ammonium
salts thereof as well as the anhydrides of the cis-dicarboxylic
acids. Suitable examples include maleic acid, maleic anhydride,
itaconic acid, mesaconic acid, fumaric acid and citraconic acid.
Maleic anhydride and itaconic acid are the preferred
monoethylenically unsaturated dicarboxylic acid monomer(s).
[0068] The acid monomers suitable for use in this invention may be
in their acid forms or in the form of the alkali metal salts or
ammonium salts of the acid. Suitable bases useful for neutralizing
the monomer acids include sodium hydroxide, ammonium hydroxide,
potassium hydroxide, and the like. The acid monomers may be
neutralized to a level of from 0 to 50% and, preferably, from 0 to
about 20%. In many cases, the carboxylic acid monomers may be used
in the completely neutralized form. The monomers may be neutralized
prior to or during polymerization.
[0069] Preferred are neutralized carboxylic acid monomers or
anhydrides.
[0070] Preferred initiator compounds are those, wherein n is 0 or
1;
[0071] R.sub.1, R.sub.2, R.sub.3 are each independently of one
another NO.sub.2, cyano, --(R.sub.9)COOR.sub.4,
--CONR.sub.5R.sub.6, --C(O)--R.sub.7, --OR.sub.8, carbamoyl,
di(C.sub.1-C.sub.18alkyl)carbamoy- l,
--C(.dbd.NR.sub.5)(NHR.sub.6); unsubstituted C.sub.1-C.sub.18alkyl,
C.sub.7-C.sub.9phenylalkyl or C.sub.3-C.sub.12cycloalkyl; or
C.sub.1-C.sub.18alkyl, C.sub.7-C.sub.9phenylalkyl or
C.sub.3-C.sub.12cycloalkyl, which are substituted by amino,
hydroxy, cyano, carboxy, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or
phenyl, which are unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, halogen, cyano, hydroxy, carboxy,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or
R.sub.2 and R.sub.3, together with the linking carbon atom, form a
C.sub.3-C.sub.12 cycloalkyl radical; R.sub.4 is,
C.sub.1-C.sub.18alkyl, phenyl, an alkali metal cation or a
tetraalkylammonium cation; R.sub.5 and R.sub.6 are hydrogen,
C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkyl which is substituted
by at least one hydroxy group or, taken together, form a
C.sub.2-C.sub.12alkylene bridge;
[0072] R.sub.7 is hydrogen, C.sub.1-C.sub.18alkyl or phenyl;
[0073] R.sub.8 is C.sub.1-C.sub.18alkyl or C.sub.2-C.sub.18alkyl
which is substituted by at least one hydroxy group; and R.sub.9 is
C.sub.1-C.sub.4alkylen or a direct bond.
[0074] R.sub.10 is C.sub.4-C.sub.18alkyl bound via a tertiary
C-atom to the nitrogen atom, phenyl, C.sub.9-C.sub.11phenylalkyl or
C.sub.3-C.sub.12cycloalkyl;
[0075] if n is 1
[0076] R.sub.11 is C.sub.1-C.sub.18alkyl,
C.sub.7-C.sub.9phenylalkyl or C.sub.3-C.sub.12cycloalkyl or
R.sub.10 and R.sub.11 together form a C.sub.2-C.sub.12alkylene
bridge or a C.sub.2-C.sub.12alkylene bridge which is interrupted by
at least one O or N atom, which bridges are unsubstituted or
substituted with C.sub.1C.sub.18alkyl;
[0077] R.sub.12 is, unsubstituted C.sub.1-C.sub.18alkyl, phenyl,
C.sub.7-C.sub.9phenylalkyl or C.sub.3-C.sub.12cycloalkyl or
R.sub.11 and R.sub.12 together with the linking carbon atom, form a
C.sub.3-C.sub.12 cycloalkyl radical.
[0078] More preferred are initiators, wherein n is 0 or 1;
[0079] R.sub.1, R.sub.2, R.sub.3 are each independently of one
another NO.sub.2, cyano, --(R.sub.9)COOR.sub.4,
--CONR.sub.5R.sub.6, --C(O)--R.sub.7, --OR.sub.8, carbamoyl,
di(C.sub.1-C.sub.8alkyl)carbamoyl- , --C(.dbd.NR.sub.5)(NHR.sub.6);
unsubstituted C.sub.1-C.sub.12alkyl, C.sub.7-C.sub.9phenylalkyl or
C.sub.5-C.sub.7cycloalkyl; or C.sub.1-C.sub.8alkyl,
C.sub.7-C.sub.9phenylalkyl or C.sub.5-C.sub.7cycloalkyl or, which
are substituted by amino, hydroxy, cyano, carboxy,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or phenyl,
[0080] or R.sub.2 and R.sub.3, together with the linking carbon
atom, form a C.sub.5-C.sub.7cycloalkyl radical;
[0081] R.sub.4 is C.sub.1-C.sub.8alkyl, phenyl, an alkali metal
cation or a tetraalkylammonium cation;
[0082] R.sub.5 and R.sub.6 are hydrogen, C.sub.1-C.sub.8alkyl,
C.sub.2-C.sub.8alkyl which is substituted by at least one hydroxy
group or, taken together, form a C.sub.2-C.sub.6alkylene
bridge;
[0083] R.sub.7 is hydrogen, C.sub.1-C.sub.8alkyl or phenyl;
[0084] R.sub.8 is C.sub.1-C.sub.8alkyl or C.sub.2-C.sub.8alkyl
which is substituted by at least one hydroxy group;
[0085] R.sub.9 is C.sub.1-C.sub.4alkylen or a direct bond;
[0086] R.sub.10 is C.sub.4-C.sub.18alkyl bound via a tertiary
C-atom to the nitrogen atom or phenyl;
[0087] if n is 1
[0088] R.sub.11 is C.sub.1-C.sub.18alkyl, phenyl or
C.sub.7-C.sub.9phenylalkyl or
[0089] R.sub.10 and R.sub.11 together form a
C.sub.2-C.sub.12alkylene bridge or a C.sub.2-C.sub.12alkylene
bridge which is interrupted by at least one O or N atom, which
bridges are unsubstituted or substituted with
C.sub.1-C.sub.18alkyl;
[0090] R.sub.12 is unsubstituted C.sub.1-C.sub.18alkyl or
phenyl.
[0091] Particularly preferred initiators are those, wherein n is 0
or 1;
[0092] R.sub.1, R.sub.2, R.sub.3 are each independently of one
another NO.sub.2, cyano, --C(O)--R.sub.7, --OR.sub.8, unsubstituted
C.sub.1-C.sub.12alkyl or phenyl, which is unsubstituted or
substituted by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, cyano,
hydroxy, carboxy, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino;
[0093] or R.sub.2 and R.sub.3, together with the linking carbon
atom, form a C.sub.5-C.sub.7 cycloalkyl radical;
[0094] R.sub.7 is, C.sub.1-C.sub.8alkyl or phenyl;
[0095] R.sub.8 is C.sub.1-C.sub.8alkyl or C.sub.2-C.sub.8alkyl
which is substituted by at least one hydroxy group and R.sub.10 is
C.sub.4-C.sub.18alkyl bound via a tertiary C-atom to the nitrogen
atom, phenyl or C.sub.9-C.sub.11phenylalkyl;
[0096] if n is 1
[0097] R.sub.11 is C.sub.1-C.sub.12alkyl; or
[0098] R.sub.10 and R.sub.11 together form a
C.sub.2-C.sub.6alkylene bridge which is unsubstituted or
substituted with C.sub.1-C.sub.4alkyl;
[0099] R.sub.12 is hydrogen, unsubstituted C.sub.1-C.sub.4alkyl or
phenyl.
[0100] Preferably n is 0; R.sub.1 is cyano; R.sub.2 and R.sub.3 are
each independently of one another unsubstituted
C.sub.1-C.sub.12alkyl or phenyl; or R.sub.2 and R.sub.3, together
with the linking carbon atom, form a C.sub.5-C.sub.7cycloalkyl
radical; R.sub.10 is C.sub.4-C.sub.12alkyl bound via a tertiary
C-atom to the nitrogen atom, C.sub.9-C.sub.11phenylalkyl or
phenyl.
[0101] Another preferred group is wherein n is 1 R.sub.1 is cyano;
R.sub.2 and R.sub.3 are each independently of one another
unsubstituted C.sub.1-C.sub.12alkyl or phenyl;
[0102] or R.sub.2 and R.sub.3, together with the linking carbon
atom, form a C.sub.5-C.sub.7 cycloalkyl radical;
[0103] R.sub.10 is C.sub.4-C.sub.12alkyl bound via a tertiary
C-atom to the nitrogen atom, C.sub.9-C.sub.11phenylalkyl or phenyl;
or
[0104] R.sub.10 and R.sub.11 together form a
C.sub.2-C.sub.6alkylene bridge which is unsubstituted or
substituted with C.sub.1-C.sub.4alkyl; and
[0105] R.sub.12 is C.sub.1-C.sub.4alkyl.
[0106] This invention also relates to a free radical polymerization
process and polymers obtained thereby, which process overcomes many
of the problems and disadvantages of the afore mentioned prior art
processes.
[0107] This process is used for preparing an oligomer, a
cooligomer, a polymer or a copolymer -block or random- by free
radical polymerization of at least one ethylenically unsaturated
monomer or oligomer, which comprises (co)polymerizing the monomer
or monomers/oligomers in the presence of an initiator compound of
formula (I) 7
[0108] (I), under reaction conditions capable of effecting scission
of the O--C bond to form two free radicals, the radical
.cndot.CR.sub.1R.sub.2R.- sub.3 being capable of initiating
polymerization.
[0109] Preferably, the scission of the O--C bond is effected by
heating, ultrasonic treatment or exposure to actinic radiation.
[0110] To perform the scission of the O--C bond by heating, the
temperature is particularly preferably raised to more than
50.degree. C. and less than 160.degree. C.
[0111] The process may be carried out in the presence of an organic
solvent or in the presence of water or in mixtures of organic
solvents and water. Additional cosolvents or surfactants, such as
glycols or ammonium salts of fatty acids, may be present. Other
suitable cosolvents are described hereinafter.
[0112] Preferred processes use as little solvents as possible. In
the reaction mixture it is preferred to use more than 30% by weight
of monomer and initiator, particularly preferably more than 50% and
most preferrably more than 80%.
[0113] If organic solvents are used, suitable solvents or mixtures
of solvents are typically pure alkanes (hexane, heptane, octane,
isooctane), hydrocarbons (benzene, toluene, xylene), halogenated
hydrocarbons (chlorobenzene), alkanols (methanol, ethanol, ethylene
glycol, ethylene glycol monomethyl ether), esters (ethyl acetate,
propyl, butyl or hexyl acetate) and ethers (diethyl ether, dibutyl
ether, ethylene glycol dimethyl ether), or mixtures thereof.
[0114] The aqueous polymerization reactions can be supplemented
with a water-miscible or hydrophilic cosolvent to help ensure that
the reaction mixture remains a homogeneous single phase throughout
the monomer conversion. Any water-soluble or water-miscible
cosolvent may be used, as long as the aqueous solvent medium is
effective in providing a solvent system which prevents
precipitation or phase separation of the reactants or polymer
products until after all polymerization reactions have been
completed. Exemplary cosolvents useful in the present invention may
be selected from the group consisting of aliphatic alcohols,
glycols, ethers, glycol ethers, pyrrolidines, N-alkyl
pyrrolidinones, N-alkyl pyrrolidones, polyethylene glycols,
polypropylene glycols, amides, carboxylic acids and salts thereof,
esters, organosulfides, sulfoxides, sulfones, alcohol derivatives,
hydroxyether derivatives such as butyl carbitol or cellosolve,
amino alcohols, ketones, and the like, as well as derivatives
thereof and mixtures thereof. Specific examples include methanol,
ethanol, propanol, dioxane, ethylene glycol, propylene glycol,
diethylene glycol, glycerol, dipropylene glycol, tetrahydrofuran,
and other water-soluble or water-miscible materials, and mixtures
thereof. When mixtures of water and water-soluble or water-miscible
organic liquids are selected as the aqueous reaction media, the
water to cosolvent weight ratio is typically in the range of about
100:0 to about 10:90.
[0115] The initiator compound is preferably present in an amount of
0.01 mol-% to 30 mol-%, more preferably in an amount of 0.1 mol-%
to 10 mol-% and most preferably in an amount of 0.1 mol-% to 5
mol-%, based on the monomer or monomer mixture used.
[0116] When monomer mixtures or monomer/oligomer mixtures are used,
the calculation of mol-% is based on an average molecular weight of
the mixture.
[0117] Hydrophilic monomers, polymers and copolymers of the present
invention can be separated from one another or from the
polymerization reaction mixture by, for example, changing the pH of
the reaction media and by other well known conventional separation
techniques.
[0118] The polymerization temperature may range from about
50.degree. C. to about 180.degree. C., preferably from about
80.degree. C. to about 150.degree. C. At temperatures above about
180.degree. C., the controlled conversion of the monomer into
polymer decreases, and uncertain and undesirable by-products like
thermally initiated polymer are formed or destruction of the
polymerization regulator may occur. Frequently, these by-products
discolor the polymer mixture and a purification step may be
required to remove them, or they may be intractable.
[0119] Therefore the surprisingly high reactivity of the present
initiators which are already active at relatively low temperatures
leads to short reaction times. The resulting polymers are usually
colourless and they can be used in most cases without any further
purification step. This is an important advantage when industrial
scale-up is considered.
[0120] After the polymerizing step is complete, the formed
(co)polymer obtained is isolated. The isolating step of the present
process is conducted by known procedures, e.g. by distilling off
the unreacted monomer or by precipitation in a suitable nonsolvent,
filtering the precipitated polymer followed by washing and drying
the polymer.
[0121] Yet another embodiment of this invention is a process for
preparing a block copolymer involving at least two stages, which
comprises forming a polymer with alkoxyamine end groups of the
general structure of formula II 8
[0122] wherein n, R.sub.1, R.sub.2, R.sub.3, R.sub.10 R.sub.11 and
R.sub.12 are as defined above, the polymer containing the initiator
group --CR.sub.1R.sub.2R.sub.3 and having the oxyamine group
essentially attached as terminal group, and adding a further
monomer followed by heating to form a block copolymer.
[0123] The homopolymers or copolymers may also be prepared in a so
called in "situ process", which means that the compounds of formula
(I) are prepared from a radical .cndot.CR.sub.1R.sub.2R.sub.3 and a
compound of formula R.sub.10NO or 9
[0124] in the presence of an ethylenically unsaturated monomer or
oligomer. The radical .cndot.CR.sub.1R.sub.2R.sub.3 itself may be
prepared as described below, preferably from a compound which
liberates the radical upon heating. Under such conditions formation
of the compounds of formula (I), their scission and polymerization
occur simultaneously. By changing the reaction temperature
different pathways of the reaction are favored. It is important to
note, that under such reaction conditions still high conversion
rates in short reaction times and low polydispersities are
achieved.
[0125] It is also possible to add the ethylenically unsaturated
monomer or oligomer subsequently to the mixture of a radical
initiator and a compound of formula R.sub.10NO or 10
[0126] In this case a compound of formula (I) is prepared to a
certain amount, which may be up to 100% and subsequently the
monomer is added without further isolating the compound of formula
(I).
[0127] Therefore another object of the invention is a process for
preparing an oligomer, a cooligomer, a polymer or a copolymer
(block or random) by free radical polymerization of at least one
ethylenically unsaturated monomer or oligomer, which comprises
generating a free radical .cndot.CR.sub.1R.sub.2R.sub.3 (V) from a
compound capable of eliminating a neutral molecule, or undergoing
C-C bond-scission upon thermal or photochemical treatment, or by
hydrogen abstraction from a compound R.sub.1R.sub.2R.sub.3C--H in
reaction with reactive radicals, and reacting the free radical
.cndot.CR.sub.1R.sub.2R.sub.3 (V) with a compound R.sub.10NO or
11
[0128] in a solvent which does not interfere with the radical
reaction in the presence of at least one ethylenically unsaturated
monomer or oligomer.
[0129] Suitable monomers are those mentioned above. The polymer of
formula (II) may be isolated prior to the next reaction step or it
may be used without isolation, and the second monomer is added to
the reaction mixture of the first step.
[0130] Block copolymers are, for example, block copolymers of
polystyrene and polyacrylate (e.g., Poly(styrene-co-acrylate) or
Poly(styrene-co-acrylate-co-styrene). They are usefull as adhesives
or as compatibilizers for polymer blends or as polymer toughening
agents. Poly(methylmethacrylate-co- acrylate) diblock copolymers or
Poly(methylacrylate-co-acrylate-co-methacrylate) triblock
copolymers) are useful as dispersing agents for coating systems, as
coating additives (e.g. rheological agents, compatibilizers,
reactive diluents) or as resin component in coatings(e.g. high
solid paints) Block copolymers of styrene, (meth)acrylates and/or
acrylonitrile are useful plastics, elastomers and adhesives.
[0131] Furthermore, block copolymers of this invention, wherein the
blocks alternate between polar monomers and non-polar monomers, are
useful in many applications as amphiphilic surfactants or
dispersants for preparing highly uniform polymer blends.
[0132] The (co)polymers of the present invention may have a number
average molecular weight from 1000 to 400000 g/mol, preferably from
2000 to 250000 g/mol and, more preferably, from 2000 to 200000
g/mol. When produced in bulk, the number average molecular weight
may be up to 500000 (with the same minimum weights as mentioned
above). The number average molecular weight may be determined by
size exclusion chromatography (SEC), gel permeation chromatography
(GPC), matrix assisted laser desorption/ionizabon mass spectrometry
(MALDI-MS) or, if the initiator carries a group which can be easily
distinguished from the monomer(s), by NMR spectroscopy or other
conventional methods.
[0133] The (co)polymers of the present invention typically have a
low polydispersity. Preferably the polydispersity is from 1.1 to
2.2, more preferably from 1.1 to 1.9 and most preferably from 1.2
to 1.8.
[0134] Thus, the present invention also encompasses in the
synthesis novel block, multi-block, star, gradient, random,
hyperbranched and dendritic copolymers, as well as graft or
copolymers.
[0135] The polymers prepared by the present invention are useful
for following applications:
[0136] adhesives, detergents, dispersants, emulsifiers,
surfactants, defoamers, adhesion promoters, corrosion inhibitors,
viscosity improvers, lubricants, rheology modifiers, thickeners,
crosslinkers, paper treatment, water treatment, electronic
materials, paints, coatings, photography, ink materials, imaging
materials, superabsorbants, cosmetics, hair products,
preservatives, biocide materials or modifiers for asphalt, leather,
textiles, ceramics and wood.
[0137] Because the present polymerizaton is a "living"
polymerization, it can be started and stopped practically at will.
Furthermore, the polymer product retains the functional alkoxyamine
group allowing a continuation of the polymerization in a living
matter. Thus, in one embodiment of this invention, once the first
monomer is consumed in the initial polymerizing step a second
monomer can then be added to form a second block on the growing
polymer chain in a second polymerization step. Therefore it is
possible to carry out additional polymerizations with the same or
different monomer(s) to prepare multi-block copolymers.
Furthermore, since this is a radical polymerization, blocks can be
prepared in essentially any order. One is not necessarily
restricted to preparing block copolymers where the sequential
polymerizing steps must flow from the least stabilized polymer
intermediate to the most stabilized polymer intermediate, such as
is the case in ionic polymerization. Thus it is possible to prepare
a multi-block copolymer in which a polyacrylonitrile or a
poly(meth)-acrylate block is prepared first, then a styrene or
butadiene block is attached thereto, and so on.
[0138] Furthermore, there is no linking group required for joining
the different blocks of the present block copolymer. One can simply
add successive monomers to form successive blocks.
[0139] A plurality of specifically designed polymers and copolymers
are accessible by the present invention, such as star and graft
(co)polymers as described, inter alia, by C. J. Hawker in Angew.
Chemie, 1995, 107, pages 1623-1627, dendrimers as described by K.
Matyaszewski et al. in Macrmolecules 1996, Vol 29, No.12, pages
4167-4171, graft (co)polymers as described by C. J. Hawker et al.
in Macromol. Chem. Phys. 198, 155-166(1997), random copolymers as
described by C. J. Hawker in Macromolecules 1996, 29, 2686-2688, or
diblock and triblock copolymers as described by N. A. Listigovers
in Macromolecules 1996, 29, 8992-8993.
[0140] Yet another object of the present invention is a polymer or
oligomer, having at least one initiator group
--CR.sub.1R.sub.2R.sub.3 and at least one oxyamine group of formula
(IIa) 12
[0141] wherein n, R.sub.1, R.sub.2, R.sub.3, R.sub.10 R.sub.11 and
R.sub.12 have the meanings and preferred meanings as defined above,
obtainable by the process as defined above.
[0142] In another of its aspects, this invention relates to a
compound of formula (I) 13
[0143] wherein n is 0 or 1
[0144] R.sub.1, R.sub.2, R.sub.3 are each independently of one
another hydrogen, halogen, NO.sub.2, cyano, --CONR.sub.5R.sub.6,
--(R.sub.9)COOR.sub.4, --C(O)--R.sub.7, --OR.sub.8, --SR.sub.8,
--NHR.sub.8, --N(R.sub.8).sub.2, carbamoyl,
di(C.sub.1-C.sub.18alkyl)carb- amoyl,
--C(.dbd.NR.sub.5)(NHR.sub.6);
[0145] unsubstituted C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom; or
[0146] C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkenyl,
C.sub.2-C.sub.18 alkynyl, C.sub.7-C.sub.9phenylalkyl,
C.sub.3-C.sub.12cycloalkyl or C.sub.3-C.sub.12cycloalkyl containing
at least one nitrogen or oxygen atom, which are substituted by
NO.sub.2, halogen, amino, hydroxy, cyano, carboxy,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or
[0147] phenyl, naphthyl, which are unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, halogen, cyano, hydroxy, carboxy,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or
R.sub.2 and R.sub.3, together with the linking carbon atom, form a
C.sub.3-C.sub.12 cycloalkyl radical, a (C.sub.4-C.sub.12
cycloalkanon)-yl radical or a C.sub.3-C.sub.12cycloalky- l radical
containing at least one O atom and/or a NR.sub.8 group; or if n is
1 14
[0148] R.sub.4 is hydrogen, C.sub.1-C.sub.18alkyl, phenyl, an
alkali metal cation or a tetraalkylammonium cation;
[0149] R.sub.5 and R.sub.6 are hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkyl which is substituted by at least one hydroxy
group or, taken together, form a C.sub.2-C.sub.12alkylene bridge or
a C.sub.2-C.sub.12-alkylene bridge interrupted by at least one O
or/and NR.sub.8 atom;
[0150] R.sub.7 is hydrogen, C.sub.1-C.sub.18alkyl or phenyl;
[0151] R.sub.8 is hydrogen, C.sub.1-C.sub.18alkyl or
C.sub.2-C.sub.18alkyl which is substituted by at least one hydroxy
group;
[0152] R.sub.9 is C.sub.1-C.sub.12alkylen or a direct bond;
[0153] R.sub.10 is C.sub.4-C.sub.18alkyl bound via a tertiary
C-atom to the nitrogen atom, C.sub.9-C.sub.11phenylalkyl,
C.sub.3-C.sub.12cycloalky- l or C.sub.3-C.sub.12cycloalkyl
containing at least one nitrogen or oxygen atom; or
C.sub.4-C.sub.18alkyl bound via a tertiary C-atom to the nitrogen
atom, C.sub.9-C.sub.11phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom, which are substituted by NO.sub.2, halogen, amino,
hydroxy, cyano, carboxy, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or
[0154] phenyl, naphthyl, which are unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, halogen, cyano, hydroxy, carboxy,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or a
polycyclic cycloaliphatic ring system or a polycyclic
cycloaliphatic ring system with at least one di- or trivalent
nitrogen atom;
[0155] if n is 1
[0156] R.sub.11 is C.sub.1-C.sub.18alkyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom; or
[0157] C.sub.1-C.sub.18alkyl, C.sub.7-C.sub.9phenylalkyl,
C.sub.3-C.sub.12cycloalkyl or C.sub.3-C.sub.12cycloalkyl containing
at least one nitrogen or oxygen atom, which are substituted by
NO.sub.2, halogen, amino, hydroxy, cyano, carboxy,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or
phenyl, naphthyl, which are unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, halogen, cyano, hydroxy, carboxy,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or a
polycyclic cycloaliphatic ring system or a polycyclic
cycloaliphatic ring system with at least one di- or trivalent
nitrogen atom; or
[0158] R.sub.10 and R.sub.11 together form a
C.sub.2-C.sub.12alkylene bridge, a C.sub.3-C.sub.12alkylen-on
bridge or a C.sub.2-C.sub.12alkylene bridge which is interrupted by
at least one O or N atom, which bridges are unsubstituted or
substituted with C.sub.1-C.sub.18alkyl,
hydroxy(C.sub.1-C.sub.4)alkyl, phenyl, C.sub.7-C.sub.9phenylalkyl,
NO.sub.2, halogen, amino, hydroxy, cyano, carboxy,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino, or
[0159] R.sub.12 is hydrogen, --(R.sub.9)COOR.sub.4, cyano,
--OR.sub.8, --SR.sub.8, --NHRa, --N(R.sub.8).sub.2,
--NH--C(O)--R.sub.8, unsubstituted C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom; or
[0160] C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkenyl,
C.sub.2-C.sub.18 alkynyl, C.sub.7-C.sub.9phenylalkyl,
C.sub.3-C.sub.12cycloalkyl or C.sub.3-C.sub.12cycloalkyl containing
at least one nitrogen or oxygen atom, which are substituted by
NO.sub.2, halogen, amino, hydroxy, cyano, carboxy,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or
[0161] phenyl, naphthyl, which are unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, halogen, cyano, hydroxy, carboxy,
C.sub.1-C.sub.4alkylamino, di(C.sub.1-C.sub.4alkyl)amino; or
R.sub.11 and R.sub.12 together with the linking carbon atom, form a
C.sub.3-C.sub.12 cycloalkyl radical;
[0162] with the proviso that
[0163] if n is 0 R.sub.10 is different from the group
--CR.sub.1R.sub.2R.sub.3, and if R.sub.1 is CN and R.sub.2 and
R.sub.3 are methyl, R.sub.10 is not phenyl, phenyl substituted by
methyl, 2,4,6-trimethyl, chlor, fluor, (3-methyl,4-fluor),
(3-fluor, 4-methyl), (4-fluor, 2-methyl), (4-fluor, 2-methoxy),
(2-fluor, 3,5-methyl), 2,5-di-tert.butyl, nitro, 3,5-dinitro or 2
(--O--C(CH.sub.3).sub.2CN) 4-nitro; and
[0164] if n is 1, R.sub.12 is hydrogen, R.sub.10 phenyl or benzyl
and R.sub.11 yl,
[0165] R.sub.1, R.sub.2 and R.sub.3 are not a group
--C(CH.sub.3).sub.2CN, --C(CH.sub.3).sub.2COOCH.sub.3, benzyl,
methylbenzyl, dimethylbenzyl, 15
[0166] and the compound according to formula I is not 16
[0167] Preferred compounds are those wherein n is 0 or 1;
[0168] R.sub.1, R.sub.2, R.sub.3 are each independently of one
another NO.sub.2, cyano, --C(O)--R.sub.7, --OR.sub.8, unsubstituted
C.sub.1-C.sub.12alkyl or phenyl, which is unsubstituted or
substituted by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, cyano,
hydroxy, carboxy, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino;
[0169] or R.sub.2 and R.sub.3, together with the linking carbon
atom, form a C.sub.5-C.sub.7 cycloalkyl radical;
[0170] R.sub.7 is, C.sub.1-C.sub.8alkyl or phenyl;
[0171] R.sub.8 is C.sub.1-C.sub.8alkyl or C.sub.2-C.sub.8alkyl
which is substituted by at least one hydroxy group and R.sub.10 is
C.sub.4-C.sub.18alkyl bound via a tertiary C-atom to the nitrogen
atom, phenyl or C.sub.9-C.sub.11phenylalkyl;
[0172] if n is 1
[0173] R.sub.11 is C.sub.1-C.sub.18alkyl,
C.sub.7-C.sub.9phenylalkyl or C.sub.3-C.sub.12cycloalkyl or
R.sub.10 and R.sub.11 together form a C.sub.2-C.sub.6alkylene
bridge which is unsubstituted or substituted with
C.sub.1-C.sub.4alkyl;
[0174] R.sub.12 is, unsubstituted C.sub.1-C.sub.4alkyl or
phenyl.
[0175] Particularly preferred are compounds wherein n is 0;
[0176] R.sub.1 is cyano;
[0177] R.sub.2 and R.sub.3 are each independently of one another
unsubstituted C.sub.1-C.sub.12alkyl or phenyl; or R.sub.2 and
R.sub.3, together with the linking carbon atom, form a
C.sub.5-C.sub.7 cycloalkyl radical; R.sub.10 is
C.sub.4-C.sub.12alkyl bound via a tertiary C-atom to the nitrogen
atom or C.sub.9-C.sub.11iphenylalkyl.
[0178] Another particularly preferred group of compounds are those
wherein n is 1;
[0179] R.sub.1 is cyano;
[0180] R.sub.2 and R.sub.3 are each independently of one another
unsubstituted C.sub.1-C.sub.12alkyl or phenyl; or R.sub.2 and
R.sub.3, together with the linking carbon atom, form a
C.sub.5-C.sub.7 cycloalkyl radical; R.sub.10 is
C.sub.4-C.sub.12alkyl bound via a tertiary C-atom to the nitrogen
atom, C.sub.9-C.sub.11phenylalkyl or phenyl; or
[0181] R.sub.10 and R.sub.11 together form a
C.sub.2-C.sub.6alkylene bridge which is unsubstituted or
substituted with C.sub.1-C.sub.4alkyl; and
[0182] R.sub.12 is C.sub.1-C.sub.4alkyl.
[0183] Further meanings and preferrences for the different
substitutents R.sub.1 to R.sub.12 are mentioned before.
[0184] The invention is also directed to a compound of formula (IV)
17
[0185] wherein n is 0 or 1
[0186] R.sub.1, R.sub.2, R.sub.3 are each independently of one
another hydrogen, halogen, NO.sub.2, cyano, --CONR.sub.5R.sub.6,
--(R.sub.9)COOR.sub.4, --C(O)--R.sub.7, --OR.sub.8, --SR.sub.8,
--NHR.sub.8, --N(R.sub.8).sub.2, carbamoyl,
di(C.sub.1-C.sub.18alkyl)carb- amoyl, --C(.dbd.NR.sub.5)(NHR6);
[0187] unsubstituted C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom; or
[0188] C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkenyl,
C.sub.2-C.sub.18 alkynyl, C.sub.7-C.sub.9phenylalkyl,
C.sub.3-C.sub.12cyctoalkyl or C.sub.3-C.sub.12cycloalkyl containing
at least one nitrogen or oxygen atom, which are substituted by
NO.sub.2, halogen, amino, hydroxy, cyano, carboxy,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or
[0189] phenyl, naphthyl, which are unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, halogen, cyano, hydroxy, carboxy,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or
R.sub.2 and R.sub.3, together with the linking carbon atom, form a
C.sub.3-C.sub.12 cycloalkyl radical, a (C.sub.4-C.sub.12
cycloalkanon)-yl radical or a C.sub.3-C.sub.12cycloalky- l radical
containing at least one O atom and/or a NR.sub.8 group; or if n is
1 18
[0190] R.sub.4is hydrogen, C.sub.1-C.sub.18alkyl, phenyl, an alkali
metal cation or a tetraalkylammonium cation;
[0191] R.sub.5 and R.sub.6 are hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkyl which is substituted by at least one hydroxy
group or, taken together, form a C.sub.2-C.sub.12alkylene bridge or
a C.sub.2-C.sub.12-alkylene bridge interrupted by at least one O
or/and NR.sub.8 atom;
[0192] R.sub.7 is hydrogen, C.sub.1-C.sub.18alkyl or phenyl;
[0193] R.sub.8 is hydrogen, C.sub.1-C.sub.18alkyl or
C.sub.2-C.sub.18alkyl which is substituted by at least one hydroxy
group;
[0194] R.sub.9 is C.sub.1-C.sub.12alkylen or a direct bond;
[0195] R.sub.10 is C.sub.4-C.sub.18alkyl bound via a tertiary
C-atom to the nitrogen atom, C.sub.9-C.sub.11phenylalkyl,
C.sub.3-C.sub.12cycloalky- l or C.sub.3-C.sub.12cycloalkyl
containing at least one nitrogen or oxygen atom; or
C.sub.4-C.sub.18alkyl bound via a tertiary C-atom to the nitrogen
atom, C.sub.9-C.sub.11phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom, which are substituted by NO.sub.2, halogen, amino,
hydroxy, cyano, carboxy, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylamino or
di(C.sub.1-C.sub.4alkyl)amino; or
[0196] phenyl, naphthyl, which are unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, halogen, cyano, hydroxy, carboxy,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or a
polycyclic cycloaliphatic ring system or a polycyclic
cycloaliphatic ring system with at least one di- or trivalent
nitrogen atom;
[0197] if n is 1
[0198] R.sub.11 is C.sub.1-C.sub.18alkyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom; or
[0199] C.sub.1-C.sub.18alkyl, C.sub.7-C.sub.9phenylalkyl,
C.sub.3-C.sub.12cycloalkyl or C.sub.3-C.sub.12cycloalkyl containing
at least one nitrogen or oxygen atom, which are substituted by
NO.sub.2, halogen, amino, hydroxy, cyano, carboxy,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or
[0200] phenyl, naphthyl,, which are unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, halogen, cyano, hydroxy, carboxy,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or a
polycyclic cycloaliphatic ring system or a polycyclic
cycloaliphatic ring system with at least one di- or trivalent
nitrogen atom; or
[0201] R.sub.10 and R.sub.11 together form a
C.sub.2-C.sub.12alkylene bridge, a C.sub.3-C.sub.12alkylen-on
bridge or a C.sub.2-C.sub.12alkylene bridge which is interrupted by
at least one O or N atom, which bridges are unsubstituted or
substituted with C.sub.1-C.sub.18alkyl,
hydroxy(C.sub.1-C.sub.4)alkyl, phenyl, C.sub.7-C.sub.9phenylalkyl,
NO.sub.2, halogen, amino, hydroxy, cyano, carboxy,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino;
[0202] R.sub.12 is hydrogen, --(R.sub.9)COOR.sub.4, cyano,
--OR.sub.8, --SR.sub.8, --NHR.sub.8, --N(R.sub.8).sub.2,
--NH--C(O)--R.sub.8, unsubstituted C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl containing at least one nitrogen or
oxygen atom; or
[0203] C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkenyl,
C.sub.2-C.sub.18 alkynyl, C.sub.7-C.sub.9phenylalkyl,
C.sub.3-C.sub.12cycloalkyl or C.sub.3-C.sub.12cycloalkyl containing
at least one nitrogen or oxygen atom, which are substituted by
NO.sub.2, halogen, amino, hydroxy, cyano, carboxy,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or
[0204] phenyl, naphthyl, which are unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylthio, halogen, cyano, hydroxy, carboxy,
C.sub.1-C.sub.4alkylamino,
[0205] di(C.sub.1-C.sub.4alkyl)amino; or
[0206] R.sub.11 and R.sub.12 together with the linking carbon atom,
form a C.sub.3-C.sub.12cycloalkyl radical;
[0207] with the proviso that
[0208] if n is 0 R.sub.10 is different from the group
--CR.sub.1R.sub.2R.sub.3, and if R.sub.1 is CN and R.sub.2 and
R.sub.3 are methyl, R.sub.10 is not phenyl, phenyl substituted by
methyl, 2,4,6-trimethyl, chlor, fluor, (3-methyl,4-fluor),
(3-fluor, 4-methyl), (4-fluor, 2-methyl), (4-fluor, 2-methoxy),
(2-fluor, 3,5-methyl), 2,5-di-tert.butyl, nitro, 3,5-dinitro or 2
(--O--C(CH.sub.3).sub.2CN) 4-nitro; and
[0209] if n is 1, R.sub.12 is hydrogen, R.sub.10 phenyl or benzyl
and R.sub.11 phenyl, R.sub.1, R.sub.2 and R.sub.3 are not a group
--C(CH.sub.3).sub.2CN, --C(CH.sub.3).sub.2COOCH.sub.3, benzyl,
methylbenzyl, dimethylbenzyl, 19
[0210] and the compound according to formula IV is not 20
[0211] Meanings and preferences for the different substitutents
R.sub.1 to R.sub.12 are already mentioned.
[0212] A further object of the present invention is a process for
preparing a compound of formula (I) 21
[0213] by generating a free radical .cndot.CR.sub.1R.sub.2R.sub.3
(V) from a compound capable of eliminating a neutral molecule, or
undergoing C-C bond-scission upon thermal or photochemical
treatment, or by hydrogen abstraction from a compound
R.sub.1R.sub.2R.sub.3C--H in reaction with reactive radicals, and
reacting the free radical .cndot.CR.sub.1R.sub.2R.- sub.3 (V) with
a compound of formula R.sub.10NO or 22
[0214] in a solvent which does not interfere with the radical
reaction.
[0215] Examples for neutral molecules which can be eliminated are
N.sub.2 or O.sub.2. Reactive radicals which are able to abstract
hydrogen are for example alkoxy radicals.
[0216] Suitable solvents are aromatic, aliphatic or cycloaliphatic
hydrocarbons, such as toluene, benzene xylene, octane or
cyclohexane, ethers, such as dioxane, tetrahydrofurane or
dibutylether, alcohols, glycols or esters and amides of carboxylic
acids.
[0217] The free radical .cndot.CR.sub.1R.sub.2R.sub.3 is preferably
prepared by heating or irradiation of a compound of formula IIIa,
IIIb or IIIc 23
[0218] Preferably the radical .cndot.CR.sub.1R.sub.2R.sub.3 is
prepared by a thermal reaction at a temperature from 40.degree. to
150.degree. C., more preferrably from 60.degree. to 150.degree. C.
and most preferrably from 70.degree. to 140.degree. C. R.sub.1,
R.sub.2 and R.sub.3 have the meanings and preferred meanings
defined above.
[0219] Nitrones of formula (VI) can be prepared according to known
methods.
[0220] Examples of 5-membered nitrones are for example described by
J. B. Bapat and D. St. C. Black in Aust. J. Chem. 21, 2483 (1968).
Typical examples are mentioned below. 24
[0221] Further nitrones are described by H. Gnichtel, K. E.
Schuster in Chem. Ber. 111, 1171 (1978). 25
[0222] A. G. Krainev, T. D. Williams, D. J. Bigelow describe in J.
Magnet. Res., B 111, 272 (1996) the preparation of following
nitrones. 26
[0223] Examples of 6-membered nitrones are for example described by
Shun-Ishi Murahashi et al. in J. Org. Chem. 55 1736 (1990). 27
[0224] These nitrones may be reacted with the appropriate reactive
radical .cndot.CR.sub.1R.sub.2R.sub.3 to obtain compounds of
formula (I).
[0225] Some reaction products between nitrones and reactive
radicals have been reported and are listed below.
[0226] M. Iwamura, N. Inamoto: Bull. Chem. Soc. Japan 43,856
(1970): 28
[0227] or D. A. Becker: J.Am. Chem. Soc. 118, 905 (1996). 29
[0228] M. lwamura, N. lnamoto: Bull. Chem. Soc. Japan 43, 860
(1970) have reported the preparation of the following compound.
30
[0229] None of these compounds have been used to polymerize
ethylenically unsaturated monomers or oligomers.
[0230] The production of C-centered radicals is described, inter
alia, in Houben Weyl, Methoden der Organischen Chemie, Vol. E 19a,
pages 60-147. These methods can be applied in general analogy.
[0231] The reaction of reacting radicals with nitroso compounds is
known per se and described by B. A. Gingras et al. in J. Chem. Soc.
page 1920,1954.
[0232] Most preferably, the free radical source is
2,2'-azobisisobutyronit- rile, 2,2'-azobis(2-methylbutyronitrile),
2,2'-azobis(2,4-dimethylvaleroni- trile),
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile),
1,1'-azobis(1-cyclohexanecarbonitrile), 2,2'-azobis(isobutyramide)
dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile,
dimethyl-2,2'-azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile,
2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane),
2,2'-azobis(N,N'-dimethyleneisobutyramidine), free base or
hydrochloride, 2,2'-azobis(2-amidinopropane), free base or
hydrochloride,
2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide}
or
2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamid-
e.
[0233] These compounds are commercially available.
[0234] If more than one radical source is used, a mixture of
substitution patterns is obtainable. This invention also relates to
the use of an initiator compound of formula (I) for polymerizing
ethylenically unsaturated monomers.
[0235] The alkoxyamines of formula (I) may be prepared and isolated
as described above. However, it is also possible to produce the
compounds of formula (I) in situ during polymerization by adding a
compound of formula IV, which has been isolated as intermediate in
the process described before, to the polymerizable monomers and by
adding, also in situ, the corresponding radical initiator.
[0236] Consequently a further aspect of the invention is a
polymerizable composition, comprising
[0237] a) at least one ethylenically unsaturated monomer or
oligomer;
[0238] b) a compound of formula (IV) and
[0239] c) a radical initiator as described above capable of
generating a free radical of formula (V) 31
[0240] wherein n, R.sub.1, R.sub.2, R.sub.3, R.sub.10, R.sub.11 and
R.sub.12 are as defined above including their preferences.
[0241] Still another aspect of the invention is a process for
preparing an oligomer, a cooligomer, a polymer or a copolymer
(block or random) by free radical polymerization of at least one
ethylenically unsaturated monomer/oligomer, which comprises
subjecting a composition as described above to heat or actinic
radiation.
[0242] A further aspect of the present invention is the use of a
compound of formula I for polymerizing ethylenically unsaturated
monomers.
[0243] Suitable initiators are those listed above including their
preferrences.
[0244] The following Examples illustrate the invention in more
detail.
[0245] A) Examples for the preparation of N,N,O-trisubstituted
hydroxylamines (table 1)
[0246] Example A1. Preparation of)
N-(1,3,3-tetramethyl-butyl)-N,O-bis-(1--
cyano-1-methyl-ethyl)-hydroxylamin compound (101).
[0247] 8,6 g (0,06 mol) 1-nitroso-1,1 ,3,3-tetramethyl-butan
(prepared according to Org. Synth. 65, 166 (1986)) and 24,9 g (0,15
mol) azobis-isobutyronitril are dissolved in 100 ml benzene. After
careful purge with argon the solution is refluxed for 2 hours under
argon atmosphere. Benzene is distilled off on the rotary evaporator
and the residue is diluted with 100 ml hexane. The precipitated
2,3-dimethyl-succinicacid dinitrile was removed by filtration. The
filtrate is evaporated and subjected to column chromatography on
silica gel (hexane-ethylacetate 9:1). 14,8 g (88%) of the compound
of formula (101) are obtained as viscous oil.
[0248] Example A2. Preparation of
N-(1,1,3,3-tetramethyl-butyl)-N,O-bis-(1-
-cyano-cyclohexyl)-hydroxylamin (102). 1,4 g (0,01 Mol)
1-nitroso-1,1,3,3-tetramethyl-butan and 4,9 g (0.02 Mol)
azobis-(1-cyanocyclohexane) are dissolved in 25 ml chlorbenzene.
After careful purge with argon the solution is heated to
100.degree. C. for 3 hours under argon atmosphere. Chlorbenzene is
distilled off on the rotary evaporator. The residue subjected to
column chromatography on silica gel (hexane/ethylacetate 9:1) and
recrystallyzed from hexane. 1.45 g (39%) of the compound of formula
(102) are obtained.
1TABLE 1 C(%), H(%), N(%) Nr. compound mp. (.degree. C.)
calc./found 101 32 viscous oil 68,78; 10,46; 15,04/ 68,79; 10,34;
15,04 102 33 108-112 73,49; 10,37; 11,69/ 73.39; 10,43; 11,66 104
34 V-65 35 V-70 36
[0249] Example A3. Preparation of
1-(1-cyano-1-methyl-ethoxy)-2-(1-cyano-1-
-methyl-ethyl)-2,5,5-tetra-methyl-pyrrolidin (105).
[0250] 16 g (0.125 Mol)2,5,5-trimethyl-pyrrolin-1-oxid [prepared
according to M. J. Turner et al.: Synth. Commun. 16 (11), 1377
(1986)] and 37 g (0.225 Mol) azobis-isobutyronitril are dissolved
in 150 ml benzene. After careful purge with argon the solution is
refluxed for 6 hours under argon atmosphere. Benzene is distilled
off on the rotary evaporator and the residue is diluted with 100 ml
hexane. The precipitated 2,3-dimethyl-succinicacid dinitrile was
removed by filtration. The filtrate is evaporated and subjected to
column chromatography on silica gel (hexane/ethylacetate 9:1). 9,6
g (29%) of the compound of formula (101) are obtained, m.p.
65-69.degree. C.
[0251] Example A4: Preparation of
1-(1-cyano-cyclohexyloxy)-2-(1-cyano-cyc-
lohexyl)-2,4,4-tetra-methyl-pyrrolidin (106).
[0252] 7.65 g ( 0.06 Mol) 2,4,4-trimethyl-pyrrolin-1-oxid [prepared
according to M. J. Turner et al.: Synth. Commun. 16 (11),1377
(1986)] and 22 g (0.09 Mol) azobis-(1-cyanocyclohexan) are
dissolved in 75 ml chlorbenzene. After careful purge with argon the
solution is heated to 100.degree. C. for 8,5 hours under argon
atmosphere. Chlorbenzene is distilled off on the rotary evaporator.
The residue subjected to column chromatography on silica gel
(hexane/ethylacetate 9:1) and recrystallyzed from
dichlormethane/hexane. 10,1 g (49%) of the compound of formula
(102) are obtained, m.p. 124.degree.-127.degree. C.
2TABLE 2 C(%), H(%), N(%) Nr. Compound m.p. (.degree. C.) Ber./Gef.
105 37 65-69 68.40 9.57 15.95 68.34 9.47 15.91 106 38 124-127 73.43
9.68 12.23 73.27 9.26 12.23 107 39
[0253] Compounds V-65 and V-70 (WACO) are commercially
available.
[0254] B) Polymerizations using compounds of Table I and Table 2 as
initiators
[0255] General remarks:
[0256] Solvents and monomers are distilled over a Vigreux column
under argon atmosphere or under vacuum, shortly before being
used.
[0257] To remove oxygen all polymerization reaction mixtures are
flushed before polymerization with argon and evacuated under vaccum
applying a freeze-thaw cycle. The reaction mixtures are then
polymerized under argon atmosphere.
[0258] At the start of the polymerization reaction, all starting
materials are homogeneously dissolved.
[0259] Conversion is determined by removing unreacted monomers from
the polymer at 80.degree. C. and 0.002 torr for 30 minutes,
weighing the remaining polymer and subtract the weight of the
initiator.
[0260] Characterization of the polymers is carried out by MALDI-MS
(Matrix Assisted Laser Desorption Ionization Mass Spectrometry)
and/or GPC (Gel Permeation Chromatography).
[0261] MALDI-MS: Measurements are performed on a linear TOF (Time
Of Flight) MALDI-MS LDI-1700 Linear Scientific Inc., Reno, USA. The
matrix is 2,5-dihydroxybenzoic acid and the laser wavelength is 337
nm.
[0262] GPC: Is performed using RHEOS 4000 of FLUX INSTRUMENTS.
Tetrahydrofurane (THF) is used as a solvent and is pumped at 1
ml/min. Two chromatography columns are put in series: type Plgel 5
.mu.m mixed-C of POLYMER INSTRUMENTS, Shropshire, UK. Measurements
are performed at 40.degree. C. The columns are calibrated with low
polydispersity polystyrenes having Mn from 200 to 2000000 Dalton.
Detection is carried out using a RI-Detector ERC-7515A of ERCATECH
AG at 30.degree. C.
[0263] Example B1. Polymerization of n-butylacrylate using compound
101
[0264] In a 50 ml three neck flask, equipped with thermometer,
cooler and magnetic stirrer, 654 mg ( 2.34 mmol) of compound 101
and 20 g ( 156 mmol) of n-butylacrylate are mixed and degased. The
clear solution obtained is heated under argon to 120.degree. C.
Polymerization starts spontaneously and the temperature rises to
143.degree. C. After 15 minutes, the exothermal reaction slowly
stops and the viscosity of the solution increases. The reaction
mixture is stirred for an additional 10 minutes at 145.degree. C.
and is then cooled to 80.degree. C. The remaining monomer is
removed by evaporation under high vacuum. 19.1 g (95%) of the
initial monomer have reacted. A clear colourless viscous fluid is
obtained.
[0265] MALDI-MS: Mn=3400, Mw=6100, PD=1.8
[0266] Example B2. Polymerization of n-butylacrylate using comround
102 in xylene
[0267] In a 100 ml three neck flask, equipped with thermometer,
cooler and magnetic stirrer, 841 mg (2.34 mmol) of compound 102, 20
g (156 mmol) of n-butylacrylate and 10 g xylene are mixed and
degased. The clear solution obtained is heated under argon to
130.degree. C. Polymerization starts spontaneously and the
temperature rises to 141.degree. C. After 10 minutes, the
exothermal reaction slowly stops. The reaction mixture is then
cooled to room temperature. The remaining monomer and solvent is
removed by evaporation at 80.degree. C. under high vacuum. 18.1 g
(87%) of the initial monomer have reacted. A clear colourless
viscous fluid is obtained.
[0268] GPC: Mn=7400, Mw=14800, PD=2
[0269] Example B3. Polymerization of n-butylacrylate using compound
101 in octane.
[0270] In a 50 ml three neck flask, equipped with thermometer,
cooler and magnetic stirrer, 279 mg (1.75 mmol) of compound 101 and
15 g ( 117 mmol) of n-butylacrylate in 7,5g octane are mixed and
degased. The clear solution obtained is heated under argon to
130.degree. C. Polymerization starts spontaneously. After 15
minutes, the exothermal reaction slowly stops and the viscosity of
the solution increases. The reaction mixture is stirred for an
additional 2.5 h at 130.degree. C. and is then cooled to 80.degree.
C. The remaining monomer is removed by evaporation under high
vacuum. 14.0 g (93%) of the initial monomer have reacted. A clear
colorless viscous fluid is obtained.
[0271] GPC analysis: Mn 8500, Mw: 15300, Polydispersity (PD):
1.8
[0272] Example B4. Polymerization of n-butylacrylate using compound
102 in toluene.
[0273] 631 mg (1.8 mmol) of compound 102, 15 g (117 mmol)
n-butylacrylat and 7.5 g toluene are reacted at 110.degree. C. for
2.5 h. After evaporation of volatile components 14.8 g (95%)
polymer are obtained.
[0274] GPC: Mn=7100, Mw=13200, PD=1.8
[0275] Example B5. Polymerization of n-butylacrylate using compound
102 in heptane.
[0276] 1.4 g (3.9 mmol) of compound 102, 5 g (39 mmol)
n-butylacrylate and 2.5 g heptane are reacted at 100.degree. C. for
22 h. After evaporation of volatile components 5.9 g (91%) of
viscous liquid are obtained.
[0277] GPC: Mn=1300, Mw=2100, PD=1.6
[0278] Example B6. Polymerization of methylmethacrylate (MMA) using
compound 102 in toluene.
[0279] 808 mg (2.25 mmol) of compound 102, 15 g (150 mmol) MMA and
7.5 g toluene are reacted at 110.degree. C. for 2.5 h. After
evaporation of volatile components 9.2 g (61%) of a solid white
foam are obtained.
[0280] GPC: Mn=3000, Mw=5800, PD=1.9
[0281] Example B7. Polymerization of methacrylic acid
-2-diamino-ethylester (MADMAEE) using compound 102 in heptane.
[0282] 686 mg (1.91 mmol) of compound 102, 20 g (127 mmol) MADMAEE
and 10 g heptane are reacted at 100.degree. C. for 5 h. After
evaporation of volatile components 13.1 g (66%) of a partially
solid material are obtained.
[0283] GPC: Mn=4300, Mw=7400, PD=1.7
[0284] Example B8. Polymerization of methacryic acid-glycidylester
(MAGE) using compound 102 in dioxane.
[0285] 1.52 g (4.22 mmol) of compound 102, 20 g (141 mmol) MAGE and
10 g dioxane are reacted at 100.degree. C. for 1 h. After
evaporation of volatile components 13.9 g (62%) of a viscous
material are obtained.
[0286] GPC: Mn=3800, Mw=6100, PD=1.6
[0287] Example B9. Polymerization of acrylic
acid-4-hvdroxybutylester using comgound 102 in dioxane.
[0288] 1.66 g (4.6 mmol) of compound 102, 22.2 g (154 mmol) of
acrylic acid-4-hydroxybutylester and 11.1 g dioxane are reacted at
105.degree. C. for 2.5 h. After evaporation of volatile components
20.1 g (83%) of a viscous material are obtained.
[0289] GPC: Mn=4000, Mw=7100, PD=1.8
[0290] Example B10. Polymerization of acrylic
acid-(3-sulfopropylester) Kalium-salt using compound 102.
[0291] 0.232 g (0.65mmol) of compound 102, 10 g (43 mmol) acrylic
acid-(3-sulfopropylester) Kalium-salt, 90 g ethylenglykol and 10 g
water are mixed, degassed and heated to 90.degree. C. The mixture
is reacted for 20 h. The clear polymer solution is poured into
aceton. The white solid polymer is filtered off and dried under
high vacuum. 5.8 g (56%) are obtained. .sup.1H-NMR in D.sub.2O
shows no acrylate double bond between 6-6.5 ppm, thus indicating
that all monomer has reacted.
[0292] Example B11. Random copolymer from n-butylacrylate and
methacrylic acid -2-diamino ethylester (MADMAEE) using compound
102.
[0293] 1.37 g (3.81 mmol) of compound 102, 16.3 g (127 mmol) of
n-butylacrylate, 20 g (127 mmol) of MADMAEE and 18 g octane are
reacted at 130.degree. C. for 2.5 h. After evaporation of volatile
components 30.7 g (85%) copolymer are obtained.
[0294] GPC: Mn=5300, Mw=9200, PD=1.7
[0295] Example B12. Random copolymer from n-butylacrylate and
methylmethacrylate using compound 102.
[0296] 2.17 g (6.03 mmol) of compound 102, 7 g (70.3 mmol)
methylmethacrylate and 10 g (70.3 mmol) of n-butylacrylate in 8.5 g
dioxane are degassed and reacted at 105.degree. C. for 5 h under
argon. After evaporation of volatile components 15 g (75%)
copolymer are obtained.
[0297] GPC: Mn=2200, Mw=3800, PD=1.7
[0298] Example B13. Blockcopolymer from n-butylacrylate and acrylic
acid-2-ethoxyethylester 3 g (8.34 mmol) of compound 102, 17.8 g
(139 mmol) n-butylacrylate and 9 g toluene are reacted at
115.degree. C. for 2,5 h. After evaporation of volatile components
13.9 g (61%) polymer are obtained. 20 g (139 mmol) acrylic
acid-2-ethoxyethylester and 19 g toluene are added. The mixture is
reacted at 115.degree. C. for 2,5 h. After evaporation of volatile
components 33.4 g (98%, based on the second monomer) copolymer are
obtained. Total conversion is 60%.
[0299] GPC: Mn=3900, Mw=7800, PD=2
[0300] Example B14. Blockcogolymer from n-butylacrylate and acrylic
acid-3-hydroxypropylester 3 g (8.34 mmol) of compound 102, 17.8 g
(139 mmol) n-butylacrylate and 9 g dioxane are reacted at
105.degree. C. for 2,5 h. After evaporation of volatile components
15.2 g (69%) polymer are obtained. 18.1 g (139 mmol) acrylic
acid-3-hydroxypropylester and 18 g dioxane are added. The mixture
is reacted at 105.degree. C. for 2 h. After evaporation of volatile
components 33.8 g (100% , based on the second monomer) copolymer
are obtained. Total conversion is 69%.
[0301] GPC: Mn=3300, Mw=11500, PD=3.5
[0302] Example B15. Blockcopolymer from n-butylacrylate and acrylic
acid
[0303] 1.85 g (5.1 mmol) of compound 102, 20 g (156 mmol)
n-butylacrylate and 10 g octane are reacted at 130.degree. C. for
2,5 h. After evaporation of volatile components 21.3 g (97%)
polymer are obtained. 1.12 g (15.6 mmol) acrylic acid and 11 g
dioxane are added. The mixture is reacted at 105.degree. C. for 2.5
h. After evaporation of volatile components 22.3 g (89%, based on
the second monomer) copolymer are obtained.
[0304] GPC: Mn=4200, Mw=6500, PD=1.6
[0305] Example B16. Blockcopolymer from n-butylacrylate and
methylmethacrylate
[0306] 3.08 g (8.58 mmol) of compound 102, 20 g (156 mmol)
n-butylacrylate and 10 g octane are reacted at 130.degree. C. for
2,5 h. After evaporation of volatile components 22.7 g (98%)
polymer are obtained. 15.6 g (156 mmol) methylmethacrylate and 10 g
octane are added. The mixture is reacted at 130.degree. C. for 2.5
h. After evaporation of volatile components 29.4 g copolymer are
obtained. Total conversion is 43%.
[0307] GPC: Mn=2600, Mw=3900, PD=1.5
[0308] Example B17. Blockcopolymer from n-butylacrylate and
methacrylic acid-2-dimethylamino-ethylester/(MADMAEE)
[0309] 1.37 g (3.81 mmol) 102, 16.3 g (127 mmol) n-butylacrylate
and 18 g octane are reacted at 130.degree. C. for 2.5 h. Volatile
components are evaporated and 20 g (127 mmol) MADMAEE in 18 g
octane are added and reacted at 130.degree. C. for 2.5 h. After
evaporation of volatile components 30.3 g (80%) of blockcopolymer
are obtained.
[0310] GPC: Mn=4800, Mw=9700, PD=2
[0311] Example B18. Homololymerization of styrene using compound
102
[0312] In a 50 ml flask 0.719 g (2 mmol) of compound 102, 20.9 g
(200 mmol) styrene and 20 g toluene are mixed. The mixture is
refluxed and polymerized for 6 h. After evaporation of volatile
components 9.73 g (47 %) polymer are obtained.
[0313] GPC: Mn=3100, Mw=4900, PD=1.6
[0314] Example B19. In situ preparation of initiator from compound
104 and azobisisobutyronitrile and simultaneous polymerization of
n-butylacrylate
[0315] 0.447 g (3.12 mmol) 104, 0.512 (3.12 mmol)
azobisisobutyronitrile (AIBN), 20 g (156 mmol) n-butylacrylate and
10 g octane are mixed in a 100 ml flask and degassed. The mixture
is reacted at 80.degree. C. for 2 h under stirring. Temperature is
slowly raised to 130.degree. C. Polymerization is conducted at
130.degree. C. for 2.5 h. After evaporation of volatile components
5.1 g (21%) polymer are obtained.
[0316] GPC: Mn=1200, Mw=1700, PD=1.4
[0317] Example B20. In situ preparation of initiator from compound
104 and V-65 with simultaneous polymerization of
n-butylacrylate
[0318] 0.670 g (4.7 mmol) of compound 104, 1.162 g (4.7 mmol) of
compound V-65, 30 g (234 mmol) n-butylacrylate and 15 9 octane are
mixed in a 100 ml flask and degased. The mixture is stirred for 30
min. at 800.degree. C. The temperature is slowly raised to
130.degree. C. The mixture is polymerized at 130.degree. C. for 2.5
h. After evaporation of volatile components 11.4 g polymer are
obtained, corresponding to 38% conversion.
[0319] GPC: Mn=2800, Mw=5700, PD=2.0
[0320] Example B21. In situ preparation of initiator from compound
104 and V-65 with subsequent polymerization of n-butylacrylate
[0321] 0.670g (4.7 mmol) of compound 104, 2.034 g (8.2 mmol) of
compound V-65 and 15 g octane are mixed in a 100 ml flask and
degased. The mixture is stirred for 1.25 h at 80.degree. C. 30 g
(234 mmol) of n-butylacrylate are added and the temperature is
slowly raised to 130.degree. C. The mixture is polymerized at this
temperature for 3 h. After evaporation of volatile components 80%
conversion are obtained.
[0322] GPC: Mn=6200, Mw=12200, PD=1.97
[0323] Example B22. Polymerization of n-butylacrylate using
compound 105
[0324] In a 50 ml three neck flask, equipped with thermometer,
cooler and magnetic stirrer, 1643 mg (6,24 mmol) of compound 101
and 20 g (156 mmol) of n-butylacrylate are mixed and degased. The
clear solution obtained is heated under argon to 115.degree. C.
Polymerization starts spontaneously and the temperature rises to
130.degree. C. After 15 minutes, the exothermal reaction slowly
stops and the viscosity of the solution increases. The reaction
mixture is stirred for an additional 15 minutes at 145.degree. C.
and is then cooled to 80.degree. C. The remaining monomer is
removed by evaporation under high vacuum. 19,3 g (97%) of the
initial monomer have reacted. A clear colourless viscous fluid is
obtained.
[0325] MALDI-MS: Mn=3000, Mw=5300, PD=1,7
[0326] GPC: Mn=3100, Mw=5400, PD=1,7
[0327] Example B23. Polymerization of n-butylacrylate using
compound 106
[0328] In a 50 ml three neck flask, equipped with thermometer,
cooler and magnetic stirrer, 804 mg (2,34 mmol) of compound 102 and
20 g (156 mmol) of n-butylacrylate are mixed and degased. The clear
solution obtained is heated under argon to 145.degree. C.
Polymerization starts spontaneously and the temperature rises to
170.degree. C. After 15 minutes, the exothermal reaction slowly
stops and the viscosity of the solution increases. The reaction
mixture is stirred for an additional 15 minutes at 145.degree. C.
and is then cooled to 80.degree. C. The remaining monomer is
removed by evaporation under high vacuum. 19,5 g (98%) of the
initial monomer have reacted. A clear colourless viscous fluid is
obtained.
[0329] MALDI-MS: Mn=4600, Mw=7300, PD=1,6
[0330] Example B24. Polymerization of n-butylacrylate using
compound 106
[0331] 1608 mg ( 4.68 mmol) of compound 106 and 20 g (156 mmol)
n-butylacrylate in 10 ml n-octane are reacted at 130.degree. C. for
2.5 h. After evaporation of volatile components 17.1 9 (79%)
polymer are obtained.
[0332] GPC: Mn=3400, Mw=5700, PD=1.7
[0333] Example B25. Polymerization of acrylic
acid-2-ethoxyethylester using compound 105
[0334] 1.96 g (4.16 mmol) of compound 105, 20 g (139 mmol) acrylic
acid-2-ethoxyethylester in 10 g toluene are polymerized in a 50 ml
flask at 115.degree. C. for 5 h. After evaporation of volatile
components 17.4 9 (87%) of a viscous polymer are obtained.
[0335] GPC: Mn=3900, Mw=7600, PD=1.9
[0336] Example B26. Polymerization of methacrylic
acid-2-dimethylaminoethy- lester using compound 106
[0337] 1.309 g (3.81 mmol) of compound 106, 20 g (127 mmol)
methacrylic acid-2-dimethylaminoethylester and 10 g octane are
reacted at 130.degree. C. for 2.5 h. After evaporation of volatile
components 18.4 g (92%) of a viscous to solid polymer is
obtained.
[0338] GPC: Mn=4100, Mw=8300, PD=2
[0339] Example B27. Blockcopolymerization of n-butylacrylate and
methacrylic acid-2-dimethylamino-ethylester using compound 106
[0340] 2.411 g (7.02 mmol) of compound 106 and 20 g (156 mmol)
n-butylacrylate, dissolved in 10 g n-cctane, are reacted at
130.degree. C. for 2.5 h. Volatile components are evaporated under
vacuum at 80.degree. C. and the residue is isolated. Conversion is
93%. In a second step 12.3 g (78 mmol) methacrylic
acid-2-dimethylaminoethylester and 16 g n-octane are added and at
130.degree. C. for 2.5 h polymerized. After evaporation of volatile
components 29.8 g (92%) copolymer are obtained.
[0341] GPC: Mn=4200, Mw=8600, PD=2
[0342] Example B28. Blockcopolymerization of n-butylacrylate and
iso-butylacrylate using compound 105
[0343] 1.233 g (4.68 mmol) of compound 105 and 20 g (156 mmol)
n-butylacrylate are reacted at 130.degree. C. for 40 min. The
reaction mixture is cooled down to 100.degree. C. and 20 g (156
mmol) iso-butylacrylate are added. Reaction is continued at
130.degree. C. for 1.5 h. After evaporation of volatile components
34.7 g (87%) copolymer are obtained.
[0344] GPC: Mn=6200, Mw=11600, PD=1.8
[0345] Example B29. Random copolymer of n-butylacrylate and
methacrylic acid-2-dimethylaminoethylester usinq compound 106
[0346] 2.617 g (7.62 mmol) of compound 106, 16.3 g (127 mmol)
n-butylacrylaet, 20 g (127 mmol) methacrylic
acid-2-dimethylaminoethylest- er and 18 g octane are reacted at
130.degree. C. for 2,5 h. After evaporation of volatile components
36.4 g (93%) of a viscous liquid are obtained.
[0347] GPC: Mn=3800, Mw=5800, PD=1.5
[0348] Example B30. Block-copolymer of n-butylacrylat and
methacrylic acid-2-dimethylaminoethylester (MADMAEE) using compound
106
[0349] 2,617 g (7.62 mmol) of compound 106 in 8.2 g octane and 16.3
g (127 mmol) n-butylacrylate are polymerized at 130.degree. C. for
2.5 h. After evaporation of volatile components 17.8 g (93%) of the
first polymer block are obtained. 18 g octane and 20 g (127 mmol)
MADMAEE are subsequently polymerized at 130.degree. C. for 2.5 h.
After evaporation of volatile components 36.3 g (93%) of the
block-copolymer are obtained.
[0350] GPC: Mn=3300, Mw=11300, PD=3.4
[0351] Example B31. Random copolymer of n-butylacrylate and acrylic
acid using compound 105
[0352] 1.3 g (4.93 mmol) of compound 105, 18.9 g (147.8 mmol)
n-butylacrylate, 1.18 g (16.4 mmol) acrylic acid in 10 g octane are
reacted at 130.degree. C. for 2.5 h. After evaporation of volatile
components 20.7 g (97%) of a clear viscous liquid are obtained.
[0353] GPC: Mn=3800, Mw=8200, PD=2.2
[0354] Example B32. Triblock-copolymer of
n-butylacrylate/methacrylic
acid-2-dimethylaminoethylester/n-butylacrylate using compound
106
[0355] 3.617 g (10.53 mmol) of compound 106, 7.5 g (58.5 mmol)
n-butylacrylate, 9.2 g (58.5 mmol) MADMAEE and again 7.5 g (58.5
mmol) n-butylacrylate in octane are polymerized successively
according to example B30 at a temperature of 130.degree. C. for 2.5
h for each step. Conversions for each step are 91%, 95% and
34%.
[0356] GPC: Mn=2600, Mw=4400, PD=1.7
[0357] Example 33. Homopolymerization of styrene
[0358] 0.679 g (2 mmol) of compound 106, 20.9 g (200 mmol) styrene
and 20 g toluene are refluxed for 6 h. After evaporation of
volatile components 19.6 g (94%) polymer are obtained.
[0359] GPC: Mn=9000, Mw=10800, PD=1.2
[0360] Example B34. Homopolymerization of styrene
[0361] 0.527 g (2 mmol) of compound 105, 20.9 g (200 mmol) styrene
and 20 g toluene are refluxed for 6 h. After evaporation of
volatile components 19.6 g (94%) polymer are obtained.
[0362] GPC: Mn=9400, Mw=11400, PD=1.2
[0363] Example B35. Pseudo-block-copolymerisation of polystyrene of
example B34 with styrene
[0364] 5 g of the polymer of example 34 are mixed with 5 g styrene
and 20 g toluene. The solution is degased and reacted at
110.degree. C. for 6 h. After evaporation of volatile components
7.7 g (54%) polymer are obtained.
[0365] GPC: Mn=13500, Mw=17500, PD=1.3
[0366] Example B36. Block-copolymer of styrene and
n-butylacrylate
[0367] 62.5 g (0.6 mol) styrene are polymerized with 1.68 g (6
mmol) of compound 105 in 40 g octane at 110.degree. C. for 6 h. 42
g (66%) of polystyrene are obtained.
[0368] GPC: Mn=9400, Mw=11400, PD=1.2
[0369] To 30 9 of the polystyrene 40 g (312 mmol) n-butylacrylate
and 40 g octan are added. The mixture is heated to 130.degree. C.
for 6 h under stirring. n-butylacrylate is reacted to 98% and 69 g
of the block copolymer are obtained.
[0370] GPC: Mn=13500, Mw=19100, PD=1.4
[0371] Example B37. In situ preparation of initiator from compound
107 and azobisisobutyronitrile with simultaneous polymerization of
n-butylacrylate
[0372] In a 100 ml flask 0.397 g (3.12 mmol) of compound 107, 0.512
g (3.12 mmol) AIBN, 20 g (156 mmol) n-butylacrylate and 10 g octane
are mixed. The mixture is stirred at 80.degree. C. for 2 h. The
temperature is slowly raised to 130.degree. C. and the mixture is
reacted for 2.5 h at this temperature. After evaporation of
volatile components 17.5 g (83%) of a viscous liquid are
obtained.
[0373] GPC: Mn=6500, Mw=13200, PD=2
[0374] Example B38. In situ preparation of initiator from compound
107 and V-65 with simultaneous polymerization of
n-butylacrylate
[0375] In a 100 ml flask 0.397 g (3.12 mmol) of compound 107, 0.775
g (3.12 mmol) of compound V-65, 20 g (156 mmol) n-butylacrylate and
10 g octane are mixed. The mixture is stirred for 30 min. at
80.degree. C. Temperature is raised slowly to 130.degree. C. and
the mixture is reacted for 2.5 h. After evaporation of volatile
components 65% conversion is obtained.
[0376] GPC: Mn=5400, Mw=9200, PD=1.7
[0377] Example B39. In situ preparation of initiator from compound
107 and V-65 with subsequent polymerization of n-butylacrylate
[0378] In a 100 ml flask 0.595 g (4.7 mmol) of compound 107, 2.034
g (8.2 mmol) of compound V-65 and 15 g octane are mixed. The
mixture is stirred at 80.degree. C. for 1.25 h. 30 g (234 mmol)
n-butylacrylate are added and the temperature is slowly raised to
130.degree. C. The mixture is allowed to react for 5 h at this
temperature. After evaporation of volatile components 20%
conversion is achieved.
[0379] GPC: Mn=5800, Mw=9000, PD=1.66
[0380] Example B40. In situ preparation of initiator from compound
107 and V-70 with simultaneous polymerization of
n-butylacrylate
[0381] In a 100 ml flask 0.595 g (4.7 mmol) of compound 107, 2.526
g (8.2 mmol) of compound V-70, 30 g (234 mmol) n-butylacrylate and
15 g octane are mixed. The mixture is stirred for 15 min. at
60.degree. C. Temperature is raised slowly to 130.degree. C. and
the mixture is reacted for 5 h. After evaporation of volatile
components 66% conversion is obtained.
[0382] GPC: Mn=4400, Mw=7600, PD=1.73
[0383] Example B41. In situ preparation of initiator from compound
107 and V-70 with subsequent polymerization of n-butylacrylate
[0384] In a 100 ml flask 0.595 g (4.7 mmol) of compound 107, 2.526
g (8.2 mmol) of compound V-70 and 15 g octane are mixed. The
mixture is stirred at 60.degree. C. for 1.25 h. 30 g (234 mmol)
n-butylacrylate are added and the temperature is slowly raised to
130.degree. C. The mixture is allowed to react for 5 h at this
temperature. After evaporation of volatile components 20%
conversion is achieved.
[0385] GPC: Mn=5500, Mw=9400, PD=1.72
* * * * *