U.S. patent application number 10/450229 was filed with the patent office on 2004-04-29 for n-alkoxy-4,4-dioxy-polyalkyl-piperidine compounds, their corresponding n-oxides and controlled radical polymerization therewith.
Invention is credited to Nesvadba, Peter, Wunderlich, Wiebke, Zink, Marie-Odile.
Application Number | 20040082742 10/450229 |
Document ID | / |
Family ID | 8175080 |
Filed Date | 2004-04-29 |
United States Patent
Application |
20040082742 |
Kind Code |
A1 |
Nesvadba, Peter ; et
al. |
April 29, 2004 |
N-alkoxy-4,4-dioxy-polyalkyl-piperidine compounds, their
corresponding n-oxides and controlled radical polymerization
therewith
Abstract
The present invention relates to selected 1-alkoxy-2,2,6,6
tetramethyl piperidine, 1-alkoxy-2,2 diethyl-6,6 dimethyl
piperidine and 1-alkoxy-2,6 diethyl-2,3,6 dimethyl piperidine
derivatives which are substituted in the 4 position by two oxygen
atoms forming an open chain or cyclic ketal structure, a
polymerizable composition comprising a) at least one ethylenically
unsaturated monomer and b) said piperidine derivatives. Further
aspects of the present invention are a process for polymerizing
ethylenically unsaturated monomers, and the use of 1-alkoxy-2,2,6,6
tetramethyl piperidine, 1-alkoxy-2,2 diethyl-6,6 dimethyl
piperidine and 1-alkoxy-2,6 diethyl-2,3,6 dimethyl piperidine
derivatives which are substituted in the 4 position by two oxygen
atoms forming an open chain or cyclic ketal structure for
controlled polymerization. The intermediate N-oxyl derivatives, a
composition of the N-oxyl derivatives with ethylenically
unsaturated monomers and a free radical initiator, as well as a
porcess for polymerization are also subjects of the present
invention.
Inventors: |
Nesvadba, Peter; (Marly,
CH) ; Zink, Marie-Odile; (Mulhouse, FR) ;
Wunderlich, Wiebke; (Bologna, DE) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
8175080 |
Appl. No.: |
10/450229 |
Filed: |
June 11, 2003 |
PCT Filed: |
November 12, 2001 |
PCT NO: |
PCT/EP01/13072 |
Current U.S.
Class: |
526/217 |
Current CPC
Class: |
C07D 211/94 20130101;
C07D 519/00 20130101; C07D 491/113 20130101; C08F 2/46 20130101;
C07D 491/22 20130101; C08F 4/00 20130101 |
Class at
Publication: |
526/217 |
International
Class: |
C08F 002/00; C08F
004/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 14, 2000 |
EP |
008111908 |
Claims
1. A polymerizable composition, comprising a) at least one
ethylenically unsaturated monomer or oligomer, and b) a compound of
formula Ia, IIa or IIIa 321 wherein n is 1 or 2; X is selected from
the group consisting of --CH.sub.2-phenyl, CH.sub.3CH-phenyl,
(CH.sub.3).sub.2C-phenyl, (C.sub.5-C.sub.6cycloalkyl).sub.2CCN,
(CH.sub.3).sub.2CCN, --CH.sub.2CH.dbd.CH.sub.2,
CH.sub.3CH--CH.dbd.CH.sub.2, 3-cyclohexenyl, 3-cyclopentenyl,
(C.sub.1-C.sub.4alkyl)CR.sub.20--C(O)-phenyl,
(C.sub.1-C.sub.4)alkyl-CR.sub.20--C(O)--(C.sub.1-C.sub.4)alkoxy,
(C.sub.1-C.sub.4)alkyl-CR.sub.20--C(O)--(C.sub.1-C.sub.4)alkyl,
(C.sub.1-C.sub.4)alkyl-CR.sub.20--C(O)--N-di(C.sub.1-C.sub.4)alkyl,
(C.sub.1-C.sub.4)alkyl-CR.sub.20--C(O)--NH(C.sub.1-C.sub.4)alkyl,
(C.sub.1-C.sub.4)alkyl-CR.sub.20--C(O)--NH.sub.2, and a group of
formula 322 wherein R.sub.20 is hydrogen or (C.sub.1-C.sub.4)alkyl,
R.sub.21 is hydrogen, C.sub.1-C.sub.4alkyl or phenyl and R.sub.22
is C.sub.1-C.sub.12alkyl which is unsubstituted or substituted by
OH or N(R.sub.20)(R.sub.21) or which is interrupted by O or
NR.sub.20; if n is 1 Y and Y' are independently
C.sub.1-C.sub.12alkyl, C.sub.3-C.sub.12alkenyl,
C.sub.3-C.sub.12alkinyl, C.sub.5-C.sub.8cycloalk- yl, phenyl,
naphthyl, C.sub.7-C.sub.9phenylalkyl; or Y and Y' together form one
of the bivalent groups --C(R.sub.1)(R.sub.2)--CH(R.sub.3)--,
CH(R.sub.1)--CH.sub.2--C(R.sub.2)(R.sub.3)--,
--CH(R.sub.2)--CH.sub.2--C(- R.sub.1)(R.sub.3)--,
--CH.sub.2--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--, o-phenylene,
1,2-cyclohexyliden, --CH.sub.2--CH.dbd.CH--CH.sub.2-- or 323
wherein R.sub.1 is hydrogen, C.sub.1-C.sub.12alkyl, COOH,
COO--(C.sub.1-C.sub.12)alkyl or CH.sub.2OR.sub.4; R.sub.2 and
R.sub.3 are independently hydrogen, methyl ethyl, COOH or
COO--(C.sub.1-C.sub.12)alky- l; R.sub.4 is hydrogen,
C.sub.1-C.sub.12alkyl, benzyl, or a monovalent acyl residue derived
from an aliphatic, cycloaliphatic or aromatic monocarboxylic acid
having up to 18 carbon atoms; if n is 2 Y and Y' together form one
of the tetravalent groups 324Q is a bisacyl residue which is
derived from a C.sub.2-C.sub.12dicarboxylic acid or
C.sub.1-C.sub.12alkylene; and Z is C.sub.1-C.sub.12alkylene.
2. A polymerizable composition according to claim 1 wherein the
compound is of formula Ia or IIa.
3. A polymerizable composition according to claim 1 wherein in the
compound of formula Ia, IIa or IIIa X is selected from the group
consisting of --CH.sub.2-phenyl, CH.sub.3CH-ph nyl,
(CH.sub.3).sub.2C-phenyl, (C.sub.5-C.sub.6cycloalkyl).sub.2CCN,
(CH.sub.3).sub.2CCN, 3-cyclohexenyl and the other substituents are
as defined in claim 1.
4. A polymerizable composition according to claim 1 wherein in the
compound of formula Ia, IIa or IIIa X is CH.sub.3CH-phenyl and the
other substituents are as defined in claim 1.
5. A polymerizable composition according to claim 1 wherein in the
compound of formula Ia, IIa or IIIa X is selected from the group
consisting of --CH.sub.2-phenyl, CH.sub.3CH-phenyl,
(CH.sub.3).sub.2C-phenyl, (C.sub.5-C.sub.6cycloalkyl).sub.2CCN,
(CH.sub.3).sub.2CCN, 3-cyclohexenyl, n is 1 Y and Y' are
independently C.sub.1-C.sub.12alkyl, C.sub.3-C.sub.12alkenyl,
C.sub.3-C.sub.12alkinyl, C.sub.5-C.sub.8cycloalkyl, phenyl,
naphthyl, C.sub.7-C.sub.9phenylalkyl; or Y and Y' together form one
of the bivalent groups --C(R.sub.1)(R.sub.2)--CH(R.sub.3)--,
CH(R.sub.1)--CH.sub.2--C(R.sub.2)(R- .sub.3)--,
--CH(R.sub.2)--CH.sub.2--C(R.sub.1)(R.sub.3)--,
--CH.sub.2--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--, o-phenylene,
1,2-cyclohexyliden, --CH.sub.2--CH.dbd.CH--CH.sub.2-- or 325
wherein R.sub.1 is hydrogen, C.sub.1-C.sub.12alkyl, COOH,
COO--(C.sub.1-C.sub.12)- alkyl or CH.sub.2OR.sub.4; R.sub.2 and
R.sub.3 are independently hydrogen, methyl ethyl, COOH or
COO--(C.sub.1-C.sub.12)alkyl; R.sub.4 is hydrogen,
C.sub.1-C.sub.12alkyl, benzyl, or a monovalent acyl residue derived
from an aliphatic, cycloaliphatic or aromatic monocarboxylic acid
having up to 18 carbon atoms.
6. A polymerizable composition according to claim 5 wherein in the
compound of formula Ia, IIa or IIIa X is CH.sub.3CH-phenyl; n is 1
Y and Y' are independently C.sub.1-C.sub.12alkyl,
C.sub.3-C.sub.12alkenyl, phenyl or benzyl; or Y and Y' together
form one of the bivalent groups
--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--,
CH(R.sub.1)--CH.sub.2--C(R.sub.2)(R- .sub.3)--,
--CH(R.sub.2)--CH.sub.2--C(R.sub.1)(R.sub.3)--,
--CH.sub.2--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--,
--CH.sub.2--CH.dbd.CH--CH- .sub.2-- wherein R.sub.1 is hydrogen,
C.sub.1-C.sub.12alkyl, COO--(C.sub.1-C.sub.12)alkyl or
CH.sub.2OR.sub.4; R.sub.2 and R.sub.3 are independently hydrogen,
methyl ethyl, or COO--(C.sub.1-C.sub.12)alkyl; R.sub.4 is hydrogen,
C.sub.1-C.sub.12alkyl, benzyl, or a monovalent acyl residue derived
from an aliphatic, cycloaliphatic or aromatic monocarboxylic acid
having up to 12 carbon atoms.
6. A polymerizable composition according to claim 1 wherein the
compound of formula Ia or IIa is 1.)
2,6-Diethyl-4,4-dimethoxy-2,3,6-trimethyl-1-(-
1-phenyl-ethoxy)-piperidine 2.)
4,4-Diethoxy-2,6-diethyl-2,3,6-trimethyl-1-
-(1-phenyl-ethoxy)-piperidine 3.)
2,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl--
ethoxy)-4,4dipropoxy-piperidine 4.)
4,4-Dibutoxy-2,6-diethyl-2,3,6-trimeth-
yl-1-(1-phenyl-ethoxy)-piperidine 5.)
2,6-Diethyl-4,4-diisobutoxy-2,3,6-tr-
imethyl-1-(1-phenyl-ethoxy)-piperidine 6.)
2,6-Diethyl-2,3,6-trimethyl-4,4-
-bis-octyloxy-1-(1-phenyl-ethoxy)-piperidine 7.)
4,4-Bis-allyloxy-2,6-diet-
hyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine 8.)
4,4Bis-cyclohexyloxy-2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-pipe-
ridine 9.)
4,4-Bis-benzyloxy-2,6diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy-
)-piperidine 10.)
7,9-Diethyl-6,7,9-trimethyl-8-(1-phenyl-ethoxy)-1,4-diox-
a-8-aza-spiro[4.5]decane 11.)
7,9-Diethyl-2,6,7,9-tetramethyl-8-(1-phenyl--
ethoxy)-1,4-dioxa-8-aza-spiro[4.5]decane 12.)
2,7,9-Triethyl-6,7,9-trimeth-
yl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-spiro[4.5]decane 13.)
7,9-Diethyl-6,7,9-trimethyl-8-(1-phenyl-ethoxy)-2-propyl-1,4-dioxa-8-aza--
spiro-[4.5]decane 14.)
2-Butyl-7,9-diethyl-6,7,9-trimethyl-8-(1-phenyl-eth-
oxy)-1,4-dioxa-8-aza-spiro[4.5]decane 15.)
7,9-Diethyl-6,7,9-trimethyl-2-o-
ctyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-spiro[4.5]decan 16.)
2-Decyl-7,9-diethyl-6,7,9-trimethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-s-
piro[4.5]decane 17.)
2-Dodecyl-7,9-diethyl-6,7,9-trimethyl-8-(1-phenyl-eth-
oxy)-1,4-dioxa-8-aza-spiro-[4.5]decane 18.)
[7,9-Diethyl-6,7,9-trimethyl-8-
-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-spiro[4.5]dec-2yl-]-methanol
19.) Acetic acid
7,9-diethyl-8-hydroxy-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4-
.5]dec-2-ylmethyl ester; compound with isopropyl-benzene 20.)
Octadecanoic acid
7,9-diethyl-6,7,9-trimethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-spir-
o[4.5]dec-2-ylmethyl ester 21.) Benzoic acid
7,9-diethyl-8-hydroxy-6,7,9-t-
rimethyl-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl ster; compound
with isopropyl-benzene 22.)
7,9-Diethyl-2-methoxymethyl-6,7,9-trimethyl-8-(1-p- h
nyl-ethoxy)-1,4-dioxa-8-aza-spiro[4.5]decane 23.)
2-Cyclohexyloxymethyl-7,9-diethyl-6,7,9-trimethyl-8-(1-phenyl-ethoxy)-1,4-
dioxa-8-aza-spiro[4.5]decane 24.)
2-Benzyloxymethyl-7,9-diethyl-6,7,9-trim-
ethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-spiro[4.5]decane 25.)
Octanedioic acid
bis-[7,9diethyl-6,7,9-trimethyl-8-(1-phenyl-ethoxy)-1,di-
oxa-8-aza-spiro[4.5]dec-2-ylmethyl] ester 26.) Terephthalic acid
bis-[7,9-diethyl-6,7,9-trimethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-spir-
o[4.5]dec-2-ylmethyl] ester 27.)
1,4-Bis-{[7,9-diethyl-6,7,9-trimethyl-8-(-
1-phenyl-ethoxy)-1,4-dioxa-8-aza-spiro[4.5]dec-2-yl]-methyloxy}-butane
28.)
7,9-Diethyl-2,2,6,7,9-pentamethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-az-
a-spiro[4.5]decane 29.)
7,9-Diethyl-2,3,6,7,9-pentamethyl-8-(1-phenyl-etho-
xy)-1,4-dioxa-8-aza-spiro[4.5]decane 30.)
2,3-Benzo-7,9-diethyl-6,7,9-trim-
ethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-spiro[4.5]decane 31.)
2,3-Cyclohexano-7,9-diethyl-6,7,9-trimethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-
-8-aza-spiro[4.5]decane 32.)
7,9-Diethyl-6,7,9-trimethyl-8-(1-phenyl-ethox-
y)-1,4-dioxa-8-aza-spiro[4.5]decane-2,3-dicarboxylic acid 33.)
7,9-Diethyl-6,7,9-trimethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-spiro[4.5-
]decane-2,3-dicarboxylic acid dimethyl ester 34.)
8,10-Diethyl-7,8,10-trim-
ethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-spiro[5.5]undecane 35.)
8,10-Diethyl-3,3,7,8,10-pentamethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-s-
piro-[5.5]undecane 36.)
3,8,10-Triethyl-3,7,8,10-tetramethyl-9-(1-phenyl-e-
thoxy)-1,5-dioxa-9-aza-spiro[5.5]undecane 37.)
3,3,8,10-Tetraethyl-7,8,10--
trimethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-spiro-[5.5]undecane
38.)
8,10-Diethyl-3,7,8,10-tetramethyl-9-(1-phenyl-ethoxy)-3-propyl-1,5-dioxa--
9-aza-spiro-[5.5]undecane 39.)
3-Butyl-3,8,10-triethyl-7,8,10-trimethyl-9--
(1-phenyl-ethoxy)-1,5-dioxa-9-aza-spiro-[5.5]undecane 40.)
2,4-Diethyl-1,2,4-trimethyl-3-(1-phenyl-ethoxy)-7,16-dioxa-3aza-dispiro[5-
.2.5.2]-hexadec-11-ene 41.)
[8,10-Diethyl-3,7,8,10-tetramethyl-9-(1-phenyl-
-ethoxy)-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl]-methanol 42.)
[3,8,10-Triethyl-7,8,10-trimethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-spi-
ro[5.5]undec-3-yl]-methanol 43.)
8,10-Diethyl-3-methoxymethyl-3,7,8,10-tet-
ramethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-spiro[5.5]undecane
44.)
3-Cyclohexyloxymethyl-8,10-diethyl-3,7,8,10-tetramethyl-9-(1-phenyl-ethox-
y)-1,5-dioxa-9-aza-spiro[5.5]undecane 45.)
3-Benzyloxymethyl-8,10-diethyl--
3,7,8,10-tetramethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-spiro[5.5]undecan-
e 46.) Acetic acid
8,10-diethyl-3,7,8,10-tetramethyl-9-(1-phenyl-ethoxy)-1-
,5-dioxa-9-aza-spiro[5.5]undec-3-ylmethyl ester 47.) Octanedioic
acid
bis-[8,10-diethyl-3,7,8,10-tetramethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-az-
a-spiro[5.5]undec-3-ylmethyl] ester 48.)
1,6-Bis-{3,8,10-triethyl-7,8,10-t-
rimethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-spiro[5.5]undec-3-methyloxy}--
hexane 49.)
8,10-Diethyl-3,7,8,10-tetramethyl-9-(1-phenyl-ethoxy)-1,5-diox-
a-9-aza-spiro[5.5]-undecane-3-carboxylic acid 50.)
8,10-Diethyl-3,7,8,10-t-
etramethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-spiro[5.5]-undecane-3-carbo-
xylic acid methyl ester 51.)
8,10-Diethyl-7,8,10-trimethyl-9-(1-phenyl-eth-
oxy)-1,5-dioxa-9-aza-spiro[5.5]undecane-3,3-dicarboxylic acid
diethyl ester 52.)
3,3-Bisspiro-{8,10-diethyl-7,8,10-trimethyl-9-(1-phenyl-ethoxy-
)-1,5-dioxa-9-aza-spiro[5.5]undecane}53.)
2,4-Diethyl-1,2,4-trimethyl-3-(1-
-phenyl-ethoxy)-7,12-dioxa-3-aza-spiro[5.6]dodec-9-en 54.)
2,2-Diethyl-4,4-dimethoxy-6,6-dimethyl-1-(1-phenyl-ethoxy)-piperidine
55.)
4,4-Diethoxy-2,2-diethyl-6,6-dimethyl-1-(1-phenyl-ethoxy)-piperidine
56.)
2,2-Diethyl-6,6-dimethyl-1-(1-phenyl-ethoxy)4,4-dipropoxy-piperidine
57.)
4,4-Dibutoxy-2,2-diethyl-6,6-dimethyl-1-(1-phenyl-ethoxy)-piperidine
58.)
2,2-Diethyl-4,4-diisobutoxy-6,6-dimethyl-1-(1-phenyl-ethoxy)-piperid-
ine 59.) 2,2-Diethyl-6,6-dimethyl-4,4-bis-octyloxy-1-(1-phenyl-
thoxy)-pip ridine 60.)
4,4-Bis-allyloxy-2,2-diethyl-6,6-dimethyl-1-(1-phenyl-ethoxy)-
-piperidine 61.)
4,4-Bis-cyclohexyloxy-2,2-diethyl-6,6-dimethyl-1-(1-pheny-
l-ethoxy)-piperidine 62.)
4,4-Bis-benzyloxy-2,2diethyl-6,6-dimethyl-1-(1-p-
henyl-thoxy)-piperidine 63.)
7,7-Diethyl-9,9-dimethyl-8-(1-phenyl-ethoxy)--
1,4-dioxa-8-aza-spiro[4.5]decane 64.)
7,7-Diethyl-2,9,9-trimethyl-8-(1-phe-
nyl-ethoxy)-1,4-dioxa-8-aza-spiro[4.5]decane 65.)
2,7,7-Triethyl-9,9-dimet-
hyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-spiro[4.5]decane 66.)
7,7-Diethyl-9,9dimethyl-8-(1-phenyl-ethoxy)-2-propyl-1,4-dioxa-8-aza-spir-
o[4.5]decane 67.)
2-Butyl-7,7-diethyl-9,9dimethyl-8-(1-phenyl-ethoxy)-1,4--
dioxa-8-aza-spiro[4.5]decane 68.)
7,7-Diethyl-9,9-dimethyl-2-octyl-8-(1-ph-
enyl-ethoxy)-1,4-dioxa-8-aza-spiro[4.51]decane 69.)
2-Decyl-7,7-diethyl-9,9-dimethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-spir-
o[4.5]decane 70.)
2-Dodecyl-7,7-diethyl-9,9-dimethyl-8-(1-phenyl-ethoxy)-1-
,4-dioxa-8-aza-spiro[4.5]decane 71.)
[7,7-Diethyl-9,9-dimethyl-8-(1-phenyl-
-ethoxy)-1,4-dioxa-8-aza-spiro[4.5]dec-2-yl]-methanol 72.) Acetic
acid
7,7-diethyl-8-hydroxy-9,9-dimethyl-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmeth-
yl ester; compound with isopropyl-benzene 73.) Octadecanoic acid
7,7-diethyl-9,9-dimethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-spiro[4.5]de-
c-2-ylmethyl ester 74.) Benzoic acid
7,7-diethyl-8-hydroxy-9,9-dimethyl-1,-
4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl ester; compound with
isopropyl-benzene 75.)
7,7-Diethyl-2-methoxymethyl-9,9-dimethyl-8-(1-phen-
yl-ethoxy)-1,4-dioxa-8-aza-spiro-[4.5]decane 76.)
2-Cyclohexyloxymethyl-7,-
7diethyl-9,9-dimethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-spiro[4.5]decane
77.)
2-Benzyloxymethyl-7,7-diethyl-9,9-dimethyl-8-(1-phenyl-ethoxy)-1,4-d-
ioxa-8-aza-spiro-[4.5]decane 78.) Octanedioic acid
bis-[7,7-diethyl-9,9-di-
methyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-spiro-[4.5]dec-2-ylmethyl]
ester 79.) Terephthalic acid
bis-[7,7-diethyl-9,9-dimethyl-8-(1-phenyl-et-
hoxy)-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl] ester 80.)
1,4-Bis-{[7,7-Diethyl-9,9-dimethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-sp-
iro[4.5]dec-2-yl]-methyloxy}-butane 81.)
7,7-Diethyl-2,2,9,9-tetramethyl-8-
-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-spiro[4.5]d cane 82.) 7,7-Di
thyl-2,3,9,9-tetramethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-spiro[4.5]de-
can 83.) 2,3-Benzo-7,7-diethyl-9,9-dim
thyl-8-(1-phenyl-ethoxy)-1,4-dioxa-- 8-aza-spiro[4.5]decane 84.)
2,3-Cyclohexano-7,7-diethyl-9,9-dimethyl-8-(1--
phenyl-ethoxy)-1,4-dioxa-8-aza-spiro[4.5]decane 85.)
7,7-Diethyl-9,9dimethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-spiro[4.5]dec-
ane-2,3-dicarboxylic acid 86.)
7,7-Diethyl-9,9-dimethyl-8-(1-phenyl-ethoxy-
)-1,4-dioxa-8-aza-spiro[4.5]decane-2,3-dicarboxylic acid dimethyl
ester 87.)
8,8-Diethyl-10,10-dimethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-spiro-
[5.5]undecane 88.)
8,8-Diethyl-3,3,10,10-tetramethyl-9-(1-phenyl-ethoxy)-1-
,5dioxa-9-aza-spiro[5.5]-undecane 89.)
3,8,8-Triethyl-3,10,10-trimethyl-9--
(1-phenyl-ethoxy)-1,5-dioxa-9-aza-spiro[5.5]undecane 90.)
3,3,8,8-Tetraethyl-10,10-dimethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-spi-
ro[5.5]-undecane 91.)
8,8-Diethyl-3,10,10-trimethyl-9-(1-phenyl-ethoxy)-3--
propyl-1,5-dioxa-9-aza-spiro[5.5]undecane 92.)
3-Butyl-3,8,8-triethyl-10,1-
0-dimethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-spiro[5.5]-undecane
93.)
2,2-Diethyl-4,4-dimethyl-3-(1-phenyl-ethoxy)-7,16-dioxa-3-aza-dispiro[5.2-
.5.2]hexadec-11-ene 94.)
[8,8-Diethyl-3,10,10-trimethyl-9-(1-phenyl-ethoxy-
)-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl]-methanol 95.)
[3,8,8-Triethyl-10,10-dimethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-spiro[-
5.5]undec-3-yl]-methanol 96.)
8,8-Diethyl-3-methoxymethyl-3,10,10-trimethy-
l-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-spiro[5.5]undecane 97.)
3-Cyclohexyloxymethyl-8,8-diethyl-3,10,10-trimethyl-9-(1-phenyl-ethoxy)-1-
,5-dioxa-9-aza-spiro[5.5]undecane 98.)
3-Benzyloxymethyl-8,8-diethyl-3,10,-
10-trimethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-spiro[5.5]undecane
99.) Acetic acid
8,8-diethyl-3,10,10-trimethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-
-aza-spiro[5.5]-undec-3-ylmethyl ster 100.) Octanedioic acid
bis-[8,8diethyl-3,10,10-trimethyl-9-(1-phenyl-
thoxy)-1,5-dioxa-9-aza-spi- ro[5.5]undec-3-ylmethyl] ester 101.)
1,6-Bis{[3,8,8-triethyl-10,10-dimethy-
l-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl]-methyloxy}-hex-
ane 102.)
8,8-Diethyl-3,10,10-trimethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-az-
a-spiro[5.5]undecane-3-carboxylic acid 103.)
8,8-Diethyl-3,10,10-trimethyl-
-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-spiro[5.5]undecane-3-carboxylic
acid methyl ester 104.)
8,8-Diethyl-10,10dimethyl-9-(1-phenyl-ethoxy)-1,5-diox-
a-9-aza-spiro[5.5]undecane-3,3dicarboxylic acid diethyl ester 105.)
3,3-Bisspiro{8,8-diethyl-10,10-dimethyl-9-(1-phenyl-ethoxy)-1,5dioxa-9-az-
a-spiro[5.5]undecane}106.)
2,2-Diethyl-4,4-dimethyl-3-(1-phenyl-ethoxy)-7,-
12-dioxa-3-aza-spiro[5.6]dodec-9-ene
7. A composition according to claim 1 wherein the compound of
formula Ia or IIa is
4,4-Dibutoxy-2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-pi-
peridine;
7,9-Diethyl-6,7,9-trimethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza--
spiro[4.5]decane;
7,9-Diethyl-2,6,7,9-tetramethyl-8-(1-phenyl-ethoxy)-1,4--
dioxa-8-aza-spiro[4.5]decane;
[7,9-Diethyl-6,7,9-trimethyl-8-(1-phenyl-eth-
oxy)-1,4-dioxa-8-aza-spiro[4.5]dec-2-yl]-methanol;
8,10-Diethyl-7,8,10-tri-
methyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-spiro[5.5]undecane;
8,10-Diethyl-3,3,7,8,10-pentamethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-s-
piro[5.5]undecane;
2,4-Diethyl-1,2,4-trimethyl-3-(1-phenyl-ethoxy)-7,16-di-
oxa-3-aza-dispiro[5.2.5.2]hexadec-11-ene;
[8,10-Diethyl-3,7,8,10-tetrameth-
yl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl]-methanol
or
9-(Cyclohex-2-enyloxy)-8,10-diethyl-3,3,7,8,10-pentamethyl-1,5-dioxa-9-az-
a-spiro[5.5]undecane.
8. A composition according to claim 1, wherein the ethylenically
unsaturated monomer or oligomer is selected from the group
consisting of ethylene, propylene, n-butylene, i-butylene, styrene,
substituted styrene, conjugated dienes, acrolein, vinyl acetate,
vinylpyrrolidone, vinylimidazole, maleic anhydride, (alkyl)acrylic
acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylic esters,
(meth)acrylonitriles, (alkyl)acrylamides, vinyl halides or
vinylidene halides.
9. A composition according to claim 8, wherein the ethylenically
unsaturated monomers are ethylene, propylene, n-butylene,
i-butylene, isoprene, 1,3-butadiene,
.alpha.-C.sub.5-C.sub.18alkene, styrene, .alpha.-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.sup.-(Me.sup.+), glycidyl, unsubstituted C.sub.1-C.sub.18alkoxy,
C.sub.2-C.sub.100alkoxy interrupted by at least one N and/or O
atom, 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,
--O--CH.sub.2--CH.sub.2--N(CH.sub.3).sub.2 or
--O--CH.sub.2--CH.sub.2--N.sup.+H(CH.sub.3).sub.2 An.sup.-;
An.sup.- is a anion of a monovalent organic or inorganic acid; Me
is a monovalent metal atom or the ammonium ion. Z is oxygen or
sulfur.
10. A composition according to claim 1, wherein the compound of
formula Ia, IIa or IIIa is present in an amount of from 0.01 mol-%
to 20 mol-%,
11. 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 Ia, IIa or IIIa under
reaction conditions capable of effecting scission of the O--C bond
to form two free radicals, the radical .X being capable of
initiating polymerization.
12. A process according to claim 11, 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.
13. A compound of formula Ia, IIa or IIIa 326wherein n is 1 or 2; X
is selected from the group consisting of --CH.sub.2-phenyl,
CH.sub.3CH-phenyl, (CH.sub.3).sub.2C-phenyl,
(C.sub.5-C.sub.6cycloalkyl).- sub.2CCN, (CH.sub.3).sub.2CCN,
--CH.sub.2CH.dbd.CH.sub.2, CH.sub.3CH--CH.dbd.CH.sub.2, 3, cycloh
xenyl, 3-cyclo-pentenyl,
(C.sub.1-C.sub.4alkyl)CR.sub.20--C(O)-phenyl,
(C.sub.1-C.sub.4)alkyl-CR.s- ub.20--C(O)--(C.sub.1-C.sub.4)alkoxy,
(C.sub.1-C.sub.4)alkyl-CR.sub.20--C(- O)--(C.sub.1-C.sub.4)alkyl,
(C.sub.1-C.sub.4)alkyl-CR.sub.20--C(O)--N-di(C-
.sub.1-C.sub.4)alkyl,
(C.sub.1-C.sub.4)alkyl-CR.sub.20--C(O)--NH(C.sub.1-C- .sub.4)alkyl,
(C.sub.1-C.sub.4)alkyl-CR.sub.20--C(O)--NH.sub.2, and a group of
formula 327 wherein R.sub.20 is hydrogen or (C.sub.1-C.sub.4)alkyl,
R.sub.21 is hydrogen, C.sub.1-C.sub.4alkyl or phenyl and R.sub.22
is C.sub.1-C.sub.12alkyl which is unsubstituted or substituted by
OH or N(R.sub.20)(R.sub.21) or which is interrupted by O or
NR.sub.20; if n is 1 Y and Y' are independently
C.sub.1-C.sub.12alkyl, C.sub.3-C.sub.12alkenyl,
C.sub.3-C.sub.12alkinyl, C.sub.5-C.sub.8-cycloal- kyl, phenyl,
naphthyl, C.sub.7-C.sub.9phenylalkyl; or Y and Y' together form one
of the bivalent groups --C(R.sub.1)(R.sub.2)--CH(R.sub.3)--,
CH(R.sub.1)--CH.sub.2--C(R.sub.2)(R.sub.3)--,
--CH(R.sub.2)--CH.sub.2--C(- R.sub.1)(R.sub.3)--,
--CH.sub.2--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--, o-phenylene,
1,2-cyclohexyliden, --CH.sub.2--CH.dbd.CH--CH.sub.2-- or 328
wherein R.sub.1 is hydrogen, C.sub.1-C.sub.12alkyl, COOH,
COO--(C.sub.1-C.sub.12)alkyl or CH.sub.2OR.sub.4; R.sub.2 and
R.sub.3 are independently hydrogen, methyl ethyl, COOH or
COO--(C.sub.1-C.sub.12)alky- l; R.sub.4 is hydrogen,
C.sub.1-C.sub.12alkyl, benzyl, or a monovalent acyl residue derived
from an aliphatic, cycloaliphatic or aromatic monocarboxylic acid
having up to 18 carbon atoms; if n is 2 Y and Y' together form one
of the tetravalent groups 329Q is a bisacyl residue which is
derived from a C.sub.2-C.sub.12dicarboxylic acid or
C.sub.1-C.sub.12alkylene; and Z is C.sub.1-C.sub.12alkylene; with
the proviso that compounds A, B, C are excluded 330
14. A polymerizable composition, comprising a) at least one
ethylenically unsaturated monomer or oligomer; b) a compound of
formula Ib or IIb 331 wherein n is 1 or 2; if n is 1 Y and Y' are
independently C.sub.1-C.sub.12alkyl, C.sub.3-C.sub.12alkenyl,
C.sub.3-C.sub.12alkinyl, C.sub.5-C.sub.8cycloalkyl, phenyl,
naphthyl, C.sub.7-C.sub.9phenylalkyl; or Y and Y' together form one
of the bivalent groups --C(R.sub.1)(R.sub.2)--CH(R.sub.3)--,
CH(R.sub.1)--CH.sub.2--C(R.sub.2)(R- .sub.3)--,
--CH(R.sub.2)--CH.sub.2--C(R.sub.1)(R.sub.3)--,
--CH.sub.2--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--, o-phenylene,
1,2-cyclohexyliden, --CH.sub.2--CH.dbd.CH--CH.sub.2-- or 332
wherein R.sub.1 is hydrogen, C.sub.1-C.sub.12alkyl, COOH,
COO--(C.sub.1-C.sub.12)- alkyl or CH.sub.2OR.sub.4; R.sub.2 and
R.sub.3 are independently hydrogen, methyl ethyl, COOH or
COO--(C.sub.1-C.sub.12)alkyl; R.sub.4 is hydrogen,
C.sub.1-C.sub.12alkyl, benzyl, or a monovalent acyl residue derived
from an aliphatic, cycloaliphatic or aromatic monocarboxylic acid
having up to 18 carbon atoms; if n is 2 Y and Y' together form one
of the tetravalent groups 333Q is a bisacyl residue which is
derived from a C.sub.2-C.sub.12dicarboxylic acid or
C.sub.1-C.sub.12alkylene; and Z is C.sub.1-C.sub.12alkylene; and c)
a source of free radicals capable of initiating polymerization of
ethylenically unsaturated monomers.
15. A polymerizable composition according to claim 14 wherein in
the compound of formula Ib, IIb or IIIb n is 1 Y and Y' are
independently C.sub.1-C.sub.12alkyl, C.sub.3-C.sub.12alkenyl,
phenyl or benzyl; or Y and Y' together form one of the bivalent
groups --C(R.sub.1)(R.sub.2)--CH- (R.sub.3)--,
CH(R.sub.1)--CH.sub.2--C(R.sub.2)(R.sub.3)--,
--CH(R.sub.2)--CH.sub.2--C(R.sub.1)(R.sub.3)--,
--CH.sub.2--C(R.sub.1)(R.- sub.2)--CH(R.sub.3)--,
--CH.sub.2--CH.dbd.CH--CH.sub.2-- or; wherein R.sub.1 is hydrogen,
C.sub.1-C.sub.12alkyl, COO--(C.sub.1-C.sub.12)alkyl or
CH.sub.2OR.sub.4; R.sub.2 and R.sub.3 are independently hydrogen,
methyl ethyl, or COO--(C.sub.1-C.sub.12)alkyl; R.sub.4 is hydrogen,
C.sub.1-C.sub.12alkyl, benzyl, or a monovalent acyl residue derived
from an aliphatic, cycloaliphatic or aromatic monocarboxylic acid
having up to 12 carbon atoms.
16. A polymerizable composition according to claim 14 wherein the
compound of formula Ib or IIb is 1.) 2,6-Diethyl-4,4-dim
thoxy-2,3,6-trimethyl-pip- eridin-1-oxyl 2.)
4,4-Diethoxy-2,6-diethyl-2,3,6-trimethyl-piperidin-1-oxy- l 3.)
2,6-Diethyl-2,3,6-trimethyl-4,4-dipropoxy-piperidin-1-oxyl 4.)
4,4-Dibutoxy-2,6-diethyl-2,3,6-trimethyl-piperidin-1-oxyl 5.)
2,6-Diethyl-4,4-diisobutoxy-2,3,6-trimethyl-piperidin-1-oxyl 6.)
2,6-Diethyl-2,3,6-trimethyl-4,4-bis-octyloxy-piperidin-1-oxyl 7.)
4,4-Bis-allyloxy-2,6-diethyl-2,3,6-trimethyl-piperidin-1-oxyl 8.)
4,4-Bis-cyclohexyloxy-2,6-diethyl-2,3,6-trimethyl-piperidin-1-oxyl
9.) 4,4-Bis-benzyloxy-2,6-diethyl-2,3,6-trimethyl-piperidin-1-oxyl
10.)
7,9-Diethyl-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxyl
11.)
7,9-Diethyl-2,6,7,9-tetramethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxyl
12.)
2,7,9-Triethyl-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxy-
l 13.)
7,9-Diethyl-6,7,9-trimethyl-2-propyl-1,4-dioxa-8-aza-spiro[4.5]deca-
n-8-oxyl 14.)
2-Butyl-7,9-diethyl-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4.-
5]decan-8-oxyl 15.)
7,9-Diethyl-6,7,9-trimethyl-2-octyl-1,4-dioxa-8-aza-sp-
iro[4.5]decan-8-oxyl 16.)
2-Decyl-7,9-diethyl-6,7,9-trimethyl-1,4-dioxa-8--
aza-spiro[4.5]decan-8-oxyl 17.)
2-Dodecyl-7,9-diethyl-6,7,9-trimethyl-1,4--
dioxa-8-aza-spiro[4.5]decan-8-oxyl 18.)
7,9-Diethyl-2-hydroxymethyl-6,7,9--
trimethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxyl 19.) Acetic acid
7,9-diethyl-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl
ester-8-oxyl 20.) Octadecanoic acid
7,9-diethyl-6,7,9-trimethyl-1,4-dioxa-
-8-aza-spiro[4.5]dec-2-ylmethyl ester-8-oxyl 21.) Benzoic acid
7,9-diethyl-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl
ester-8-oxyl 22.)
7,9-Diethyl-2-methoxymethyl-6,7,9-trimethyl-1,4-dioxa-8-
-aza-spiro[4.5]decan-8-oxyl 23.)
2-Cyclohexyloxymethyl-7,9-diethyl-6,7,9-t-
rimethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxyl 24.)
2-Benzyloxymethyl-7,9-diethyl-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4.5]d-
ecan-8-oxyl 25.) Octanedioic acid
bis-(7,9-diethyl-8-oxyl-6,7,9-trimethyl--
1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl) ester 26.) Terephthalic
acid
bis-(7,9diethyl-8-oxyl-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4.5]dec-2-yl-
methyl) ester 27.)
1,4-Bis-{[7,9-diethyl-6,7,9-trimethyl-8-oxyl-1,4-dioxa--
8-aza-spiro[4.5]dec-2-yl]-methyloxy}-butane 28.)
7,9-Diethyl-2,2,6,7,9-pen-
tamethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxyl 29.)
7,9-Diethyl-2,3,6,7,9-pentamethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxyl
30.)
2,3-Benzo-7,9-diethyl-6,7,9-trimethyl-8-oxyl-1,4-dioxa-8-aza-spiro[4-
.5]decan 31.)
2,3-Cyclohexano-7,9-diethyl-6,7,9-trimethyl-8-oxyl-1,4-dioxa-
-8-aza-spiro[4.5]decane 32.)
7,9-Diethyl-6,7,9-trimethyl-1,4-dioxa-8-aza-s-
piro[4.5]decane2,3-dicarboxylic acid-8-oxyl 33.)
7,9-Diethyl-6,7,9-trimeth-
yl-1,4-dioxa-8-aza-spiro[4.5]decane-2,3-dicarboxylic acid dimethyl
ester-8-oxyl 34.)
8,10-Diethyl-7,8,10-trimethyl-1,5-dioxa-9-aza-spiro[5.5-
]undecan-9-oxyl 35.)
8,10-Diethyl-3,3,7,8,10-pentamethyl-1,5-dioxa-9-aza-s-
piro[5.5]undecan-9-oxyl 36.)
3,8,10-Triethyl-3,7,8,10-tetramethyl-1,5-diox-
a-9-aza-spiro[5.5]undecan-9-oxyl 37.)
3,3,8,10-Tetraethyl-7,8,10-trimethyl-
-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl 38.)
8,10-Diethyl-3,7,8,10-tetra-
methyl-3-propyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl 39.)
3-Butyl-3,8,10-triethyl-7,8,10-trimethyl-1,5-dioxa-9-aza-spiro[5.5]undeca-
n-9-oxyl 40.)
2,4-Diethyl-1,2,4-trimethyl-7,16-dioxa-3-aza-dispiro[5.2.5.2-
]hexadec-11-en-3-oxyl 41.)
8,10-Diethyl-3-hydroxymethyl-3,7,8,10-tetrameth-
yl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl 42.)
3,8,10-Triethyl-3-hydroxy-
methyl-7,8,10-trimethyl-1,5dioxa-9-aza-spiro[5.5]undecan-9-oxyl
43.)
8,10-Diethyl-3-methoxymethyl-3,7,8,10-tetramethyl-1,5-dioxa-9-aza-spiro[5-
.5]undecan-9-oxyl 44.)
3-Cyclohexyloxymethyl-8,10-diethyl-3,7,8,10-tetrame-
thyl-1,5-dioxa-9-aza-spiro[5.5]-undecan-9-oxyl 45.)
3-Benzyloxymethyl-8,10-diethyl-3,7,8,10-tetramethyl-1,5-dioxa-9-aza-spiro-
[5.5]undecan-9-oxyl 46.) Acetic acid
8,10-diethyl-3,7,8,10-tetramethyl-1,5-
-dioxa-9-aza-spiro[5.5]undec-3-ylmethyl ester-9-oxyl 47.)
Octanedioic acid
bis-(8,10-diethyl-9-oxyl-3,7,8,10-tetramethyl-1,5-dioxa-9-aza-spiro[5.5]u-
ndec-3-ylmethyl) ester 48.)
1,6-Bis-{3,8,10-triethyl-7,8,10-trimethyl-9-ox-
yl-1,5-dioxa-9-azaspiro[5.5]undec-3-methyloxy}-hexane 49.)
8,10-Diethyl-3,7,8,10-tetramethyl-1,5-dioxa-9-aza-spiro[5.5]undecane-3-ca-
rboxylic acid-9-oxyl 50.)
8,10-Diethyl-3,7,8,10-tetramethyl-1,5-dioxa-9-az-
a-spiro[5.5]undecane-3-carboxylic acid methyl ester-9-oxyl 51.)
8,10-Diethyl-7,8,10-trimethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-3,3-dicar-
boxylic acid diethyl ester-9-oxyl 52.)
3,3-Bisspiro-{8,10-diethyl-7,8,10-t-
rimethyl-9-oxyl-1,5-dioxa-9-aza-spiro[5.5]undecane}53.)
2,4-Diethyl-1,2,4-trimethyl-7,12-dioxa-3-aza-spiro[5.6]dodec-9-en-3-oxyl
54.) 2,2-Diethyl-4,4-dimethoxy-6,6-dimethyl-piperidin-1-oxyl 55.)
4,4-Diethoxy-2,2-diethyl-6,6-dimethyl-piperidin-1-oxyl 56.)
2,2-Diethyl-6,6-dimethyl-4,4-dipropoxy-piperidin-1-oxyl 57.)
4,4-Dibutoxy-2,2-diethyl-6,6-dimethyl-piperidin-1-oxyl 58.)
2,2-Diethyl-4,4-diisobutoxy-6,6-dimethyl-piperidin-1-oxyl 59.)
2,2-Diethyl-6,6-dimethyl-4,4-bis-octyloxy-piperidin-1-oxyl 60.)
4,4-Bis-allyloxy-2,2-diethyl-6,6-dimethyl-piperidin-1-oxyl 61.)
4,4-Bis-cyclohexyloxy-2,2-diethyl-6,6-dimethyl-piperidin-1-oxyl
62.) 4,4-Bis-benzyloxy-2,2-diethyl-6,6-dimethyl-piperidin-1-oxyl
63.)
7,7-Diethyl-9,9-dimethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxyl
64.)
7,7-Diethyl-2,9,9-trimethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxyl
65.)
2,7,7-Triethyl-9,9-dimethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxyl
66.)
7,7-Diethyl-9,9-dimethyl-2-propyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxyl
67.)
2-Butyl-7,7-diethyl-9,9-dimethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-o-
xyl 68.)
7,7-Diethyl-9,9-dimethyl-2-octyl-1,4-dioxa-8-aza-spiro[4.5]decan--
8-oxyl 69.)
2-Decyl-7,7-diethyl-9,9-dimethyl-1,4-dioxa-8-aza-spiro[4.5]dec-
an-8-oxyl 70.)
2-Dodecyl-7,7-diethyl-9,9-dimethyl-1,4-dioxa-8-aza-spiro[4.-
5]decan-8-oxyl 71.)
7,7-Diethyl-2-hydroxymethyl-9,9-dimethyl-1,4-dioxa-8-a-
za-spiro[4.5]decan-8-oxyl 72.) Acetic acid
7,7-diethyl-9,9-dimethyl-1,4-di- oxa-8-aza-spiro[4.5]dec-2-ylmethyl
ester-8-oxyl 73.) Octadecanoic acid
7,7-diethyl-9,9-dimethyl-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl
ester-8-oxyl 74.) Benzoic acid
7,7-diethyl-9,9-dimethyl-1,4-dioxa-8-aza-s- piro[4.5]dec-2-ylmethyl
ester-8-oxyl 75.) 7,7-Diethyl-2-methoxymethyl-9,9--
dimethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxyl 76.)
2-Cyclohexyloxymethyl-7,7-diethyl-9,9-dimethyl-1,4-dioxa-8-aza-spiro[4.5]-
decan-8-oxyl 77.)
2-Benzyloxymethyl-7,7-diethyl-9,9-dimethyl-1,4-dioxa-8-a-
za-spiro[4.5]decan-8-oxyl 78.) Octanedioic add
bis-(7,7-diethyl-8-oxyl-9,9-
-dimethyl-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl) ester 79.)
Terephthalic acid bis-(7,7-diethyl-8-oxyl-9,9-dim
thyl-1,4-dioxa-8-aza-sp- iro[4.5]dec-2-ylmethyl) ester 80.)
1,4-Bis-{[7,7-diethyl-9,9-dimethyl-8-ox-
yl-1,4-dioxa-8-aza-spiro[4.5]dec-2-yl]-methyloxy}-butane 81.)
7,7-Diethyl-2,2,9,9-tetramethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxyl
82.)
7,7-Diethyl-2,3,9,9tetramethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxy-
l 83.)
2,3-Benzo-7,7-diethyl-9,9-dimethyl-8-oxyl-1,4-dioxa-8-aza-spiro[4.5-
]decane 84.)
2,3-Cyclohexano-7,7diethyl-9,9-dimethyl-8-oxyl-1,4dioxa-8-aza-
spiro [4.5]decane 85.)
7,7-Diethyl-9,9dimethyl-1,4-dioxa-8-aza-spiro[4.5]d-
ecane-2,3-dicarboxylic acid-8-oxyl 86.)
7,7-Diethyl-9,9-dimethyl-1,4-dioxa-
-8-aza-spiro[4.5]decane-2,3-dicarboxylic acid dimethyl ester-8-oxyl
87.)
8,8-Diethyl-10,10-dimethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl
88.)
8,8-Diethyl-3,3,10,10-tetramethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxy-
l 89.)
3,8,8-Triethyl-3,10,10-trimethyl-1,5-dioxa-9-aza-spiro[5.5]undecan--
9-oxyl 90.)
3,3,8,8-Tetraethyl-10,10-dimethyl-1,5-dioxa-9-aza-spiro[5.5]un-
decan-9-oxyl 91.)
8,8-Diethyl-3,10,10-trimethyl-3-propyl-1,5-dioxa-9-aza-s-
piro[5.5]undecan-9-oxyl 92.)
3-Butyl-3,8,8-triethyl-10,10-dimethyl-1,5-dio-
xa-9-aza-spiro[5.5]undecan-9-oxyl 93.)
2,2-Diethyl-4,4-dimethyl-7,16-dioxa-
-3-aza-dispiro[5.2.5.2]hexadec-11-en-3-oxyl 94.)
8,8-Diethyl-3-hydroxymeth-
yl-3,10,10-trimethyl-1,5dioxa-9-aza-spiro[5.5]undecan-9-oxyl 95.)
3,8,8-Triethyl-3-hydroxymethyl-10,10-dimethyl-1,5-dioxa-9-aza-spiro[5.5]u-
ndecan-9-oxyl 96.)
8,8-Diethyl-3-methoxymethyl-3,10,10-trimethyl-1,5-dioxa-
-9-aza-spiro[5.5]undecan-9-oxyl 97.)
3-Cyclohexyloxymethyl-8,8-diethyl-3,1-
0,10-trimethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl 98.)
3-Benzyloxymethyl-8,8-diethyl-3,10,10-trimethyl-1,5-dioxa-9-aza-spiro[5.5-
]undecan-9-oxyl 99.) Acetic acid
8,8-diethyl-3,10,10-trimethyl-1,5-dioxa-9-
-aza-spiro[5.5]undec-3-ylmethyl ester-9-oxyl 100.) Octanedioic acid
bis-(8,8-diethyl-9-oxyl-3,10,10-trimethyl-1,5-dioxa-9-aza-spiro[5.5]undec-
-3-ylmethyl) ester 101.)
1,6-Bis{[3,8,8-triethyl-10,10-dimethyl-9-oxyl-1,5-
-dioxa-9-aza-spiro[5.5]undec-3-yl]-methyloxy}-hexane 102.)
8,8-Diethyl-3,10,10-trimethyl-1,5-dioxa-9-aza-spiro[5.5]undecane-3-carbox-
ylic acid-9-oxyl 103.)
8,8-Diethyl-3,10,10-trimethyl-1,5-dioxa-9-aza-spiro-
[5.5]undecane-3-carboxylic acid methyl ester-9-oxyl 104.)
8,8-Diethyl-10,10-dimethyl-1,5-dioxa-9-aza-spiro[5.5]undecane-3,3-dicarbo-
xylic acid diethyl ester-9-oxyl 105.)
3,3-Bisspiro{8,8-diethyl-10,10-dimet-
hyl-9-oxyl-1,5-dioxa-9-aza-spiro[5.5]undecane}106.)
2,2-Diethyl-4,4-dimethyl-7,12-dioxa-3-aza-spiro[5.6]dodec-9-en-3-oxyl
17. A polymerizable composition according to claim 14 wherein the
compound of formula Ib or IIb is
4,4-Dibutoxy-2,6-diethyl-2,3,6-trimethyl-piperidi- n-1-oxyl;
7,9-Diethyl-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-ox-
yl;
7,9-Diethyl-2,6,7,9-tetramethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxyl-
;
7,9-Diethyl-2-hydroxymethyl-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4.5]de-
can-8-oxyl;
8,10-Diethyl-7,8,10-trimethyl-1,5-dioxa-9-aza-spiro[5.5]undeca-
n-9-oxyl;
8,10-Diethyl-3,3,7,8,10-pentamethyl-1,5dioxa-9-aza-spiro[5.5]und-
ecan-9-oxyl;
2,4-Diethyl-1,2,4-trimethyl-7,16-dioxa-3-aza-dispiro[5.2.5.2]-
hexadec-11-en-3-oxyl;
8,10-Diethyl-3-hydroxymethyl-3,7,8,10-tetramethyl-1,-
5-dioxa-9-aza-spiro[5.5]undecan-9-oxy
18. 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 the composition according to claim 14 to heat
or actinic radiation.
19. A compound of formula Ib or IIb 334wherein n is 1 or 2; if n is
1 Y and Y' are independ ntly C.sub.1-C.sub.12alkyl,
C.sub.3-C.sub.12alkenyl, C.sub.3-C.sub.12alkinyl,
C.sub.5-C.sub.8cycloalkyl, phenyl, naphthyl,
C.sub.7-C.sub.9phenylalkyl; or Y and Y' together form one of th
bivalent groups --C(R.sub.1)(R.sub.2)--CH(R.sub.3)--,
CH(R.sub.1)--CH.sub.2--C(R.s- ub.2)(R.sub.3)--,
--CH(R.sub.2)--CH.sub.2--C(R.sub.1)(R.sub.3)--,
--CH.sub.2--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--, o-phenylene,
1,2-cyclohexyliden, --CH.sub.2--CH.dbd.CH--CH or 335 wherein
R.sub.1 is hydrogen, C.sub.1-C.sub.12alkyl, COOH,
COO--(C.sub.1-C.sub.12)alkyl or CH.sub.2OR.sub.4; R.sub.2 and
R.sub.3 are independently hydrogen, methyl ethyl, COOH or
COO--(C.sub.1-C.sub.12)alkyl; R.sub.4 is hydrogen,
C.sub.1-C.sub.12alkyl, benzyl, or a monovalent acyl residue derived
from an aliphatic, cycloaliphatic or aromatic monocarboxylic acid
having up to 18 carbon atoms; if n is 2 Y and Y' together form one
of the tetravalent groups 336Q is a bisacyl residue which is
derived from a C.sub.2-C.sub.12dicarboxylic acid or
C.sub.1-C.sub.12alkylene; and Z is C.sub.1-C.sub.12alkylene; with
the proviso that compounds D, E, F, G, H 337 are excluded.
20. A polymer or oligomer, having attached at least one oxyamine
group derived from formula Ia, IIa or IIIa according to claim
1.
21. Use of a compound of formulae Ia, IIa or IIIa according to
claim 1 for the polymerization of ethylenically unsaturated
monomers.
22. Use of a compound of formulae Ib or IIb according to claim 14
for the polymerization of ethylenically unsaturated monomers
together with a source of free radicals.
Description
[0001] The present invention relates to selected 1-alkoxy-2,2,6,6
tetramethyl piperidine, 1-alkoxy-2,2 diethyl-6,6 dimethyl
piperidine and 1-alkoxy-2,6 diethyl-2,3,6 dimethyl piperidine
derivatives which are substituted in the 4 position by two oxygen
atoms forming an open chain or cyclic ketal structure, a
polymerizable composition comprising a) at least one ethylenically
unsaturated monomer and b) said piperidine derivatives. Further
aspects of the present invention are a process for polymerizing
ethylenically unsaturated monomers, and the use of 1-alkoxy-2,2,6,6
tetramethyl piperidine, 1-alkoxy-2,2 diethyl-6,6 dimethyl
piperidine and 1-alkoxy-2,6 diethyl-2,3,6 dimethyl piperidine
derivatives which are substituted in the 4 position by two oxygen
atoms forming an open chain or cyclic ketal structure for
controlled polymerization. The intermediate N-oxyl derivatives, a
composition of the N-oxyl derivatives with ethylenically
unsaturated monomers and a free radical initiator, as well as a
process for polymerization are also subjects of the present
invention.
[0002] The compounds of the present invention provide polymeric
resin products having low polydispersity. The polymerization
process proceeds with good monomer to polymer conversion
efficiency. 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] 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 speci s capable of
polymerizing unsaturated monomers. The reactions typically have low
conversion rates. Specifically mentioned radical R'R"N--O. 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. However, the suggested
compounds do not fulfill all requirements. Particularly the
polymerization of acrylates does not proceed fast enough and/or the
monomer to polymer conversion is not as high as desired.
[0004] EP-A-0 574 666 describes some novel 1-oxyl-2,2,6,6
tetramethylpiperidin compounds and their preparation, which have an
open chain or cyclic ketal structure in the 4 position.
[0005] U.S. Pat. No. 4,105,626 discloses also nitroxides and their
preparation which are derived from 2,6-diethyl-2,6-dimethyl
piperidine which have a ketal structure in 4 position.
[0006] However none of the nitroxide and nitroxylether compounds
have been described as regulators/initiators for controlled radical
polymerization.
[0007] GB 2335190 firstly discloses polymerization
regulators/initiators on the basis of 2,2,6,6-tetraalkylpiperidine,
wherein the alkyl groups have from 1 to 6 carbon atoms and at least
one group is different from methyl. No specific compound having a
ketal structure in the 4-position is mentioned.
[0008] It has now been found, that amongst those
2,2,6,6-tetraalkylpiperid- ines generically disclosed in U.S. Pat.
No. 4,581,429 and GB 2335190 those are of particular value which
are derivatives of 1-alkoxy-2,2,6,6 tetramethyl piperidine,
1-alkoxy-2,2 diethyl-6,6 dimethyl piperidine and of 1-alkoxy-2,6
diethyl-2,3,6 dimethyl piperidine which are substituted in the 4
position by two oxygen atoms forming an open chain or cyclic ketal
structure.
[0009] The ketal structure in 4 position ensures high thermal
stability which is important for storag, particularly at elevated
temperatures. The ketal structure is thermally significantly more
stable compared to the corresponding 4-oxo compound.
[0010] The compounds exhibit an unchanged initiating/regulating
activity even after storage at elevated temperatures as for example
used in conventional stability tests.
[0011] Another problem associated with nitroxyl or nitroxyl ether
mediated free radical polymerization is the formation of a
significant color of the resulting polymer. The compounds of the
present invention which have a ketal structure in 4-position impart
significantly less color to the polymer compared to other prior art
compounds of similar structure.
[0012] The steric hindrance introduced by the two ethyl groups
instead of two methyl groups further leads to an increased
initiating activity and control of polymerization.
[0013] The particular substitution pattern in 2 and 6 position of
the piperidin ring allows high monomer to polymer conversions in
short times and low polydispersities which are generally below 2.
High monomer to polymer conversions are even achieved with
acrylates, such as ethyl- or butyl-acrylate. The temperature
necessary to achieve high conversion in short times may be for
example as low as 120.degree. C.
[0014] One subject of the present invention is a polymerizable
composition, comprising
[0015] a) at least one ethylenically unsaturated monomer or
oligomer, and
[0016] b) a compound of formula Ia, IIa or IIIa 1
[0017] wherein
[0018] n is 1 or 2;
[0019] X is selected from the group consisting of
--CH.sub.2-phenyl, CH.sub.3CH-phenyl, (CH.sub.3).sub.2C-phenyl,
(C.sub.5-C.sub.6cycloalkyl).- sub.2CCN, (CH.sub.3).sub.2CCN,
--CH.sub.2CH.dbd.CH.sub.2, CH.sub.3CH--CH.dbd.CH.sub.2,
3-cyclohexenyl, 3-cyclo-pentenyl,
(C.sub.1-C.sub.4alkyl)CR.sub.20--C(O)-phenyl,
(C.sub.1-C.sub.4)alkyl-CR.s- ub.20--C(O)--(C.sub.1-C.sub.4)alkoxy,
(C.sub.1-C.sub.4)alkyl-CR.sub.20--C(- O)--(C.sub.1-C.sub.4)alkyl,
(C.sub.1-C.sub.4)alkyl-CR.sub.20--C(O)--N-di(C-
.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.4)alkyl-CR.sub.20--C(O)--
[0020] NH(C.sub.1-C.sub.4)alkyl,
(C.sub.1-C.sub.4)alkyl-CR.sub.20--C(O)--N- H.sub.2 and a group of
formula 2
[0021] wherein
[0022] R.sub.20 is hydrogen or (C.sub.1-C.sub.4)alkyl, R.sub.21 is
hydrogen, C.sub.1-C.sub.4alkyl or phenyl and R.sub.22 is
C.sub.1-C.sub.12alkyl which is unsubstituted or substituted by OH
or N(R.sub.20)(R.sub.21) or which is interrupted by O or
NR.sub.20;
[0023] if n is 1
[0024] Y and Y' are independently C.sub.1-C.sub.12alkyl,
C.sub.3-C.sub.12alkenyl, C.sub.3-C.sub.12alkinyl,
C.sub.5-C.sub.8cycloalk- yl, phenyl, naphthyl,
C.sub.7-C.sub.9phenylalkyl; or
[0025] Y and Y' together form one of the bivalent groups
--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--,
CH(R.sub.1)--CH.sub.2--C(R.sub.2)(R- .sub.3)--,
--CH(R.sub.2)--CH.sub.2--C(R.sub.1)(R.sub.3)--,
--CH.sub.2--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--, o-phenylene,
1,2-cyclohexyliden,
[0026] --CH.sub.2--CH.dbd.CH--CH.sub.2-- or 3
[0027] wherein
[0028] R.sub.1 is hydrogen, C.sub.1-C.sub.12alkyl, COOH,
COO--(C.sub.1-C.sub.12)alkyl or CH.sub.2OR.sub.4;
[0029] R.sub.2 and R.sub.3 are independently hydrogen, methyl
ethyl, COOH or COO--(C.sub.1-C.sub.12)alkyl;
[0030] R.sub.4 is hydrogen, C.sub.1-C.sub.12alkyl, benzyl, or a
monovalent acyl residue derived from an aliphatic, cycloaliphatic
or aromatic monocarboxylic acid having up to 18 carbon atoms;
[0031] if n is 2
[0032] Y and Y' together form one of the tetravalent groups 4
[0033] Q is a bisacyl residue which is derived from a
C.sub.2-C.sub.12dicarboxylic acid or C.sub.1-C.sub.12alkylene;
and
[0034] Z is C.sub.1-C.sub.12alkylene.
[0035] Preferred is a polymerizable composition wherein the
compound is of formula Ia or IIa.
[0036] C.sub.1-C.sub.12alkyl can be linear or branched. Examples
are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl,
t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl,
t-octyl, nonyl, decyl, undecyl or dodecyl.
[0037] Alkenyl having from 3 to 12 carbon atoms is a branched or
unbranched radical, for example propenyl, 2-butenyl, 3-butenyl,
isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl,
n-2-dodecenyl, isododecenyl.
[0038] Alkinyl having from 3 to 25 carbon atoms is a branched or
unbranched radical, for example propinyl (--CH.sub.2--C.ident.CH ),
2-butinyl, 3-butinyl, n-2-octinyl or n-2-dodecinyl.
[0039] Examples of alkoxy are methoxy, ethoxy, propoxy, isopropoxy,
butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy or
octoxy.
[0040] C.sub.7-C.sub.9phenylalkyl is for example benzyl,
.alpha.-methylbenzyl, .alpha.,.alpha.-dimethylbenzyl or
2-phenylethyl, benzyl is preferred.
[0041] C.sub.1-C.sub.12alkylene is a branched or unbranched
radical, for example methylene, ethylene, propylene, trimethylene,
tetramethylene, pentamethylene, hexamethylene, heptamethylene,
octamethylene, decamethylene or dodecamethylene.
[0042] C.sub.5-C.sub.8cycloalkyl is for example cyclopentyl,
cyclohexyl, cycloheptyl, methylcyclopentyl or cyclooctyl.
[0043] Examples of a monocarboxylic acid having up to 18 carbon
atoms are formic acid, acetic acid, propionic acid, the isomers of
valeric acid, methyl ethyl acetic acid, trimethyl acetic acid,
capronic acid, lauric acid or stearic acid. Examples for
unsaturated aliphatic acids are acrylic acid, methacrylic acid,
crotonic acid, linolic acid and oleic acid.
[0044] Typical examples of cycloaliphatic carboxylic acids are
cyclohexane carboxylic acid or cyclopentane carboxylic acid.
[0045] Examples of aromatic carboxylic acids are benzoic acid,
salicylic acid or cinnamic acid.
[0046] Examples of dicarboxylic acids are oxalic acid, malonic
acid, succinic acidglutaric acid adipic acid, sebatic acid, fumaric
acid, maleic acid, phthalic acid, isophthalic acid, terephthalic
acid.
[0047] Preferred is a polymerizable composition wherein in the
compound of formula Ia, IIa or IIIa X is selected from the group
consisting of --CH.sub.2-phenyl, CH.sub.3CH-phenyl,
(CH.sub.3).sub.2C-phenyl, (C.sub.5-C.sub.6cycloalkyl).sub.2CCN,
(CH.sub.3).sub.2CCN, 3-cyclohexenyl and the other substituents are
as defined above, most preferably X is CH.sub.3CH-phenyl.
[0048] Also preferred is a polymerizable composition wherein in the
compound of formula Ia, IIa or IIIa X is selected from the group
consisting of --CH.sub.2-phenyl, CH.sub.3CH-phenyl,
(CH.sub.3).sub.2C-phenyl, (C.sub.5-C.sub.6cycloalkyl).sub.2CCN,
(CH.sub.3).sub.2CCN, 3-cyclohexenyl;
[0049] n is 1
[0050] Y and Y' are independently C.sub.1-C.sub.12alkyl,
C.sub.3-C.sub.12alkenyl, C.sub.3-C.sub.12alkinyl,
C.sub.5-C.sub.8cycloalk- yl, phenyl, naphthyl,
C.sub.7-C.sub.9phenylalkyl; or
[0051] Y and Y' together form one of the bivalent groups
--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--,
CH(R.sub.1)--CH.sub.2--C(R.sub.2)(R- .sub.3)--,
--CH(R.sub.2)--CH.sub.2--C(R.sub.1)(R.sub.3)--,
--CH.sub.2--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--, o-phenylene,
1,2-cyclohexyliden, --CH.sub.2--CH.dbd.CH--CH.sub.2-- or 5
[0052] wherein
[0053] R.sub.1 is hydrogen, C.sub.1-C.sub.12alkyl, COOH,
COO--(C.sub.1-C.sub.12)alkyl or CH.sub.2OR.sub.4;
[0054] R.sub.2 and R.sub.3 are independently hydrogen, methyl
ethyl, COOH or COO--(C.sub.1-C.sub.12)alkyl;
[0055] R.sub.4 is hydrogen, C.sub.1-C.sub.12alkyl, benzyl, or a
monovalent acyl residue derived from an aliphatic, cycloaliphatic
or aromatic monocarboxylic acid having up to 18 carbon atoms.
[0056] More preferred is a polymerizable composition wherein in the
compound of formula Ia, IIa or IIIa X is CH.sub.3CH-phenyl;
[0057] n is 1
[0058] Y and Y' are independently C.sub.1-C.sub.12alkyl,
C.sub.3-C.sub.12alkenyl, phenyl or benzyl; or
[0059] Y and Y' together form one of the bivalent groups
--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--,
CH(R.sub.1)--CH.sub.2--C(R.sub.2)(R- .sub.3)--,
--CH(R.sub.2)--CH.sub.2--C(R.sub.1)(R.sub.3)--,
--CH.sub.2--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--,
--CH.sub.2--CH.dbd.CH--CH- .sub.2-- or; wherein
[0060] R.sub.1 is hydrogen, C.sub.1-C.sub.12alkyl,
COO--(C.sub.1-C.sub.12)- alkyl or CH.sub.2OR.sub.4;
[0061] R.sub.2 and R.sub.3 are independently hydrog n, methyl
ethyl, or COO--(C.sub.1-C.sub.12)alkyl;
[0062] R.sub.4 is hydrogen, C.sub.1-C.sub.12alkyl, benzyl, or a
monoval nt acyl residu d rived from an aliphatic, cycloaliphatic or
aromatic monocarboxylic acid having up to 12 carbon atoms.
[0063] Most suitable individual compounds are given in Tables 1, 2
and 3
1TABLE 1 Compounds according to formula (Ia) 1 6
2,6-Diethyl-4,4-dimethoxy- 2,3,6-trimethyl-1-(1-phenyl-
ethoxy)-piperidine 2 7 4,4-Diethoxy-2,6-diethyl-
2,3,6-trimethyl-1-(1-phenyl- ethoxy)-piperidine 3 8
2,6-Diethyl-2,3,6-trimethyl- 1-(1-phenyl-ethoxy)-4,4-
dipropoxy-piperidine 4 9 4,4-Dibutoxy-2,6-diethyl-
2,3,6-trimethyl-1-(1-phenyl- ethoxy)-piperidine 5 10
2,6-Diethyl-4,4- diisobutoxy-2,3,6-trimethyl- 1-(1-phenyl-ethoxy)-
piperidine 6 11 2,6-Diethyl-2,3,6-trimet- hyl-
4,4-bis-octyloxy-1-(1- phenyl-ethoxy)-piperidine 7 12
4,4-Bis-allyloxy-2,6-diethyl- 2,3,6-trimethyl-1-(1-phenyl-
ethoxy)-piperidine 8 13 4,4-Bis-cyclohexyloxy-2,6-
diethyl-2,3,6-trimethyl-1-(1- phenyl-thoxy)-piperidin 9 14
4,4-Bis-benzyloxy-2,6- diethyl-2,3,6-trimethyl-1-(1-
phenyl-ethoxy)-piperidin 10 15 7,9-Diethyl-6,7,9-trimethyl-8-
(1-phenyl-ethoxy)-1,4-dioxa- 8-aza-spiro[4.5]decane 11 16
7,9-Diethyl-2,6,7,9- tetramethyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 12 17
2,7,9-Triethyl-6,7,9- trimethyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 13 18
7,9-Diethyl-6,7,9-trimethyl-8- (1-phenyl-ethoxy)-2-propyl-
1,4-dioxa-8-aza- spiro[4.5]decane 14 19 2-Butyl-7,9-diethyl-6,7,9-
trimethyl-8-(1-phenyl- ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 15
20 7,9-Diethyl-6,7,9-trimethyl- 2-octyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 16 21
2-Decyl-7,9-diethyl-6,7,9- trimethyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 17 22
2-Dodecyl-7,9-diethyl- 6,7,9-trimethyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 18 23
[7,9-Diethyl-6,7,9-trimethyl- 8-(1-phenyl-ethoxy)-1,4-
dioxa-8-aza-spiro[4.5]d c- 2-yl]-methanol 19 24 Acetic acid
7,9-diethyl-8- hydroxy-6,7,9-trimethyl-1,4-
dioxa-8-aza-spiro[4.5]dec-2- ylmethyl ester, compound with
isopropyl-benzene 20 25 Octadecanoic acid 7,9-
diethyl-6,7,9-trimethyl-8-(1- phenyl-ethoxy)-1,4-dioxa-
8-aza-spiro[4.5]dec-2- ylmethyl ester 21 26 Benzoic acid
7,9-diethyl-8- hydroxy-6,7,9-trimethyl- 1,4-dioxa-8-aza-
spiro[4.5]dec-2-ylmethyl ester; compound with isopropyl-benzene 22
27 7,9-Diethyl-2- methoxymethyl-6,7,9- trimethyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 23 28
2-Cyclohexyloxymethyl- 7,9-diethyl-6,7,9-trimethyl- -
8-(1-phenyl-ethoxy)-1,4- dioxa-8-aza- spiro[4.5]decane 24 29
2-Benzyloxymethyl-7,9- diethyl-6,7,9-trimethyl-8-(1-
phenyl-ethoxy)-1,4-dioxa- 8-aza-spiro[4.5]decane 25 30 Octanedioic
acid bis-[7,9- diethyl-6,7,9-trimethyl-8-(1-
phenyl-ethoxy)-1,4-dioxa-8- aza-spiro[4.5]dec-2-ylmethyl] ester 26
31 Terephthalic acid bis-[7,9- diethyl-6,7,9-trimethyl-8-(1- -
phenyl-ethoxy)-1,4-dioxa- 8-aza-spiro[4.5]dec-2- ylmethyl] ester 27
32 1,4-Bis-{[7,9-diethyl-6,7,9- trimethyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]dec-2-yl]- methyloxy}-butane 28
33 7,9-Diethyl-2,2,6,7,9- pentamethyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 29 34
7,9-Diethyl-2,3,6,7,9- pentamethyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 30 35
2,3-Benzo-7,9-diethyl- 6,7,9-trimethyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 31 36
2,3-Cyclohexano-7,9-diethyl- 6,7,9-trimethyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 32 37
7,9-Diethyl-6,7,9-trimethyl- 8-(1-phenyl-ethoxy)-1,4- dioxa-8-aza-
spiro[4.5]decane-2,3- dicarboxylic acid 33 38
7,9-Diethyl-6,7,9-trimethyl- 8-(1-phenyl-ethoxy)-1,4- -
dioxa-8-aza- spiro[4.5]decane-2,3- dicarboxylic acid dimethyl ester
34 39 8,10_diethyl-7,8,10- trimethyl-9-(1-phenyl-
ethoxy)-1,5-dioxa-9-aza- spiro[5.5]undecane 35 40
8,10-Diethyl-3,3,7,8,10- pentamethyl-9-(1-phenyl- -
ethoxy)-1,5-dioxa-9-aza- spiro[5.5]undecane 36 41
3,8,10-Triethyl-3,7,8,10- tetramethyl-9-(1-phenyl-
ethoxy)-1,5-dioxa-9-aza- spiro[5.5]undecane 37 42
3,3,8,10-Tetraethyl-7,8,10- trimethyl-9-(1-phenyl-
ethoxy)-1,5-dioxa-9-aza- spiro[5.5]undecane 38 43
8,10-Diethyl-3,7,8,10- tetramethyl-9-(1-phenyl-
ethoxy)-3-propyl-1,5-dioxa- 9-aza-spiro[5.5]undecane 39 44
3-Butyl-3,8,10-triethyl- 7,8,10-trimethyl-9-(1-
phenyl-ethoxy)-1,5-dioxa- 9-aza-spiro[5.5]undecane 40 45
2,4-Diethyl-1,2,4-trimethyl-3- (1-phenyl-ethoxy)-7,16- dioxa-3-aza-
dispiro[5.2.5.2]hexadec-11- ene 41 46 [8,10-Diethyl-3,7,8,10-
tetramethyl-9-(1-phenyl- ethoxy)-1,5-dioxa-9-aza-
spiro[5.5]undec-3-yl]- methanol 42 47 [3,8,10-Triethyl-7,8,10-
trimethyl-9-(1-phenyl- ethoxy)-1,5-dioxa-9-aza-
spiro[5.5]undec-3-yl]- methanol 43 48 8,10-Diethyl-3-
methoxymethyl-3,7,8,10- tetramethyl-9-(1-phenyl-
ethoxy)-1,5-dioxa-9-aza- spiro[5.5]undecane 44 49
3-Cyclohexyloxymethyl- 8,10-diethyl-3,7,8,10-
tetramethyl-9-(1-phenyl- ethoxy)1,5-dioxa-9-aza- spiro[5.5]undecane
45 50 3-Benzyloxymethyl-8,10- diethyl-3,7,8,10-
tetramethyl-9-(1-phenyl- ethoxy)-1,5-dioxa-9-aza-
spiro[5.5]undecane 46 51 Acetic acid 8,10-diethyl-
3,7,8,10-tetramethyl-9-(1- phenyl-ethoxy)-1,5-dioxa-9-
aza-spiro[5.5]undec-3- ylmethyl ester 47 52 Octanedioic acid
bis-[8,10- diethyl-3,7,8,10- tetramethyl-9-(1-phenyl-
ethoxy)-1,5-dioxa-9-aza- spiro[5.5]undec-3-ylmethyl] ester 48 53
1,6-Bis-{3,8,10-triethyl- 7,8,10-trimethyl-9-(1-
phenyl-ethoxy)-1,5-dioxa- 9-aza-spiro[5.5]undec-3-
methyloxy}-hexane 49 54 8,10-Diethyl-3,7,8,10-
tetramethyl-9-(1-phenyl)- ethoxy)-1,5-dioxa-9-aza-
spiro[5.5]undecane-3- carboxylic acid 50 55 8,10-Diethyl-3,7,8,10-
tetramethyl-9-(1-phenyl- ethoxy)-1,5-dioxa-9-aza-
spiro[5.5]undecane-3- carboxylic acid methyl ester 51 56
8,10-Diethyl-7,8,10- trimethyl-9-(1-phenyl-
ethoxy)-1,5-dioxa-9-aza- spiro[5.5]undecane-3,3- dicarboxylic acid
diethyl ester 52 57 1,6-Bis{3,8,10-triethyl-
7,8,10-trimethyl-9-(1-phenyl- ethoxy)-1,5-dioxa-9-aza-
spiro[5.5]end c-3- methyloxy}-hexane 53 58
2,4-Diethyl-1,2,4-trimethyl- 3-(1-phenyl-ethoxy)-7,12- dioxa-3-aza-
spiro[5.6]dodec-9-ene 54 59 2-(8,10-Diethyl-3,3,7,8,10-
pentamethyl-1,5-dioxa-9- aza-spiro[5.5]undec-9- yloxy)-propionic
acid 2- hydroxy-ethyl ester
[0064]
2TABLE 2 Compounds according to formula IIa 1 60
2,2-Diethyl-4,4-dimethoxy- 6,6-dimethyl-1-(1-phenyl-
ethoxy)-piperidine 2 61 4,4-Diethyloxy-2,2-diethyl-
6,6-dimethyl-1-(1-phenyl- ethoxy)-piperidine 3 62
2,2-Diethyl-6,6-dimethyl-1- (1-phenyl-ethoxy)-4,4-
dipropoxy-piperidine 4 63 4,4-Dibutoxy-2,2-diethyl-6,6-
dimethyl-1-(1-phenyl-ethoxy)- piperidine 5 64 2,2-Diethyl-4,4-
diisobutoxy-6,6-dimethyl-1- (1-phenyl-ethoxy)- piperidine 6 65
2,2-Diethyl-6,6-dimethyl-4,4- bis-octyloxy-1-(1-phenyl-
ethoxy)-piperidine 7 66 4,4-Bis-allyloxy-2,2-diethyl-
6,6-dimethyl-1-(1-phenyl- ethoxy)-piperidine 8 67
4,4-Bis-cyclohexyloxy-2,2- diethyl-6,6-dimethyl-1-(1-
phenyl-ethoxy)-piperidine 9 68 4,4-Bis-benzyloxy-2,2-
diethyl-6,6-dimethyl-1-(1- phenyl-ethoxy)-piperidine 10 69
7,7-Diethyl-9,9-dimethyl-8-(1- phenyl-ethoxy)-1,4-dioxa-8-
aza-spiro[54.5]decane 11 70 7,7-Diethyl-2,9,9-trimethyl-
8-(1-phenyl-ethoxy)-1,4- dioxa-8-aza-spiro[4.5]- decane 12 71
2,7,7-Triethyl-9,9-dimethyl- 8-(1-phenyl-ethoxy)-1,4- dioxa-8-aza-
spiro[4.5]decane 13 72 7,7-Diethyl-9,9-dimethyl-8-(1-
phenyl-ethoxy)-2-propyl-1,4- dioxca-8-aza-spiro[4.5]decane 14 73
2-Butyl-7,7-diethyl-9,9- dimethyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 15 74
7,7-Diethyl-9,9-dimethyl-2- octyl-8-(1-phenyl-ethoxy)-
1,4-dioxa-8-8-aza- spiro[4.5]decane 16 75 2-Decyl-7,7-diethyl-9,9-
dimethyl-8-(1-phenyl-ethoxy)- 1,4-dioxa-8-aza- spiro[4.5]decane 17
76 2-Dodecyl-7,7-diethyl-9,9- dimethyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 18 77
[7,7-Diethyl-9,9-dimethyl-8- (1-phenyl-ethoxy)-1,4-dioxa-
8-aza-spiro[4.5]dec-2-yl]- methanol 19 78 Acetic acid
7,7-diethyl-8- hydroxy-9,9-dimethyl-1,4-
dioxa-8-aza-spiro[4.5]dec-2- ylmethyl ester; compound with
isopropyl-benzene 20 79 Octadecanoic acid 7,7-
diethyl-9,9-dimethyl-8-(1- phenyl-ethoxy)-1,4-dioxa-
8-aza-spiro[4.5]dec-2- ylmethyl ester 21 80 Benzoic acid
7,7-diethyl-8- hydroxy-9,9-dimethyl-1,4-
dioxa-8-aza-spiro[4.5]dec-2- ylmethyl ester; compound with
isopropyl-benzene 22 81 7,7-Diethyl-2-methoxymethyl-
9,9-dimethyl-8-(1-phenyl- ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane
23 82 2-Cyclohexyloxymethyl- 7,7-diethyl-9,9-dimethyl-8-
(1-phenyl-ethoxy)-1,4- dioxa-8-aza- spiro[4.5]decane 24 83
2-Benzyloxymethyl-7,7- diethyl-9,9-dimethyl-8-(1-
phenyl-ethoxy)-1,4-dioxa-8- aza-spiro[4.5]decane 25 84 Octanedioic
acid bis-[7,7- diethyl-9,9-dimethyl-8-(1- ph nyl-
thoxy)-1,4-dioxa-8- aza-spiro[4.5]dec-2-ylmethyl] ester 26 85
Terephthalic acid bis-[7,7- diethyl-9,9-dimethyl-8-(1-
phenyl-ethoxy)-1,4-dioxa- 8-aza-spiro[4.5]dec-2- ylmethyl ester 27
86 1,4-Bis{[7,7-diethyl-9,9- dimethyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]dec-2-yl]- methyloxy}-butane 28
87 7,7-Diethyl-2,2,9,9- tetramethyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 29 88
7,7-Diethyl-2,3,9,9- tetramethyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 30 89
2,3-Benzo-7,7-diethyl-9,9- dimethyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 31 90
2,3-Cyclohexano-7,7-diethyl- 9,9-dimethyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 32 91
7,7-Diethyl-9,9-dimethyl-8- (1-phenyl-ethoxy)-1,4- dioxa-8-aza-
spiro[4.5]decane-2,3- dicarboxylic acid 33 92
7,7-Diethyl-9,9-dimethyl-8- (1-phenyl-ethoxy)-1,4-dioxa-
8-aza-spiro[4.5]decane-2,3- dicarboxylic acid dimethyl ester 34 93
8,8-Diethyl-10,10-dimethyl-9- (1-phenyl-ethoxy)-1,5-di- oxa-
9-aza-spiro[5.5]undercane 35 94 8,8-Diethyl-3,3,10,10-
tetramethyl-9-(1-phenyl- ethoxy)-1,5-dioxa-9-aza-
spiro[5.5]undecane 36 95 3,8,8-Triethyl-3,10,10-
trimethyl-9-(1-phenyl- ethoxy)-1,5-dioxa-9-aza- spiro[5.5]undecane
37 96 3,3,8,8-Tetraethyl-10,10- dimethyl-9-(1-phenyl-ethoxy)-
1,5-dioxa-9-aza- spiro[5.5]undecane 38 97 8,8-Diethyl-3,10,10-
trimethyl-9-(1-phenyl- ethoxy)-3-propyl-1,5-dioxa-
9-aza-spiro[5.5]undecane 39 98 3-Butyl-3,8,8-triethyl-10,10-
dimethyl-9-(1-phenyl- ethoxy)-1,5-dioxa-9-aza- spiro[5.5]undecane
40 99 2,2-Diethyl-4,4-dimethyl-3-(1- phenyl-ethoxy)-7,16-dioxa-3-
aza-dispiro[5.2.5.2]hexadec- 11-ene 41 100
[8,8-Diethyl-3,10,10-tri- methyl-9-(1-phenyl-eth-
oxy)-1,5-dioxa-9-aza- spiro[5.5]undec-3-yl]- methanol 42 101
[3,8,8-Triethyl-10,10- dimethyl-9-(1-phenyl-
ethoxy)-1,5-dioxa-9-aza- spiro[5.5]undec-3-yl]- methanol 43 102
8,8-Diethyl-3-methoxymethyl- 3,10,10-trimethyl-9-(1-phenyl-
ethoxy)-1,5-dioxa-9-aza- spiro[5.5]undecane 44 103
3-Cyclohexyloxymethyl- 8,8-diethyl-3,10,10- trimethyl-9-(1-phenyl-
ethoxy)-1,5-dioxa-9-aza- spiro[5.5]undecane 45 104
3-Benzyloxymethyl-8,8- diethyl-3,10,10-trimethyl-9-
(1-phenyl-ethoxy)-1,5-dioxa- 9-aza-spiro[5.5]undecane 46 105 Acetic
acid 8,8-diethyl- 3,10,10-trimethyl-9-(1-phenyl-
ethoxy)-1,5-dioxa-9-aza- spiro[5.5]undec-3-ylmethyl ester 47 106
Octandioic acid bis-[8,8- diethyl-3,10,10-trimethyl-9-
(1-phenyl-ethoxy-1,5- dioxa-9-aza- spiro[5.5]undec-3-ylmethyl]
ester 48 107 1,6-Bis{[3,8,8-triethyl-10,10- dimethyl-9-(1-phenyl-
ethoxy)-1,5-dioxa-9-aza- spiro[5.5]undec-3-yl]- methyloxy}-hexane
49 108 8,8-Diethyl-3,10,10-trimethyl- 9-(1-phenyl-ethoxy)-1,5-
dioxa-9-aza- spiro[5.5]undecane-3- carboxylic acid 50 109
8,8-Diethyl-3,10,10- trimethyl-9-(1-phenyl-
ethoxy)-1,5-dioxa-9-aza- spiro[5.5]undecane-3- carboxylic acid
methyl ester 51 110 8,8-Diethyl-10,10-dimethyl-
9-(1-phenyl-ethoxy)-1,5- dioxa-9-aza- spiro[5.5]undecane-3,3-
dicarboxylic acid diethyl ester 52 111 3,3-Bisspiro{8,8-diethyl-
10,10-dimethyl-9-(1-phenyl- ethoxy)-1,5-dioxa-9-aza-
spiro[5.5]undecane} 53 112 2,2-Diethyl-4,4-dimethyl-3-
(1-phenyl-ethoxy)-7,12- dioxa-3-aza- spiro[5.6]dodec-9-ene
[0065]
3TABLE 3 Compounds according to formula IIIa 1 113
4,4-Dimethoxy-2,2,6,6- tetramethyl-1-(1-phenyl- ethoxy)-piperidine
2 114 4,4-Diethoxy-2,2,6,6- tetramethyl-1-(1-phenyl-
ethoxy)-piperidine 3 115 2,2,6,6-Tetramethyl-1-(1-
phenyl-ethoxy)-4,4- dipropoxy-piperidine 4 116
4,4-Dibutoxy-2,2,6,6- tetramethyl-1-(1-phenyl- ethoxy)-piperidine 5
117 4,4-Diisobutoxy-2,2,6,6- tetramethyl-1-(1-phenyl-
ethoxy)-piperidine 6 118 2,2,6,6-Tetramethyl-4,4-bis-
octyloxy-1-(1-phenyl- ethoxy)-piperidine 7 119
4,4-Bis-allyloxy-2,2,6,6- tetramethyl-1-(1-phenyl-
ethoxy)-piperidine 8 120 4,4-Bis-cyclohexyloxy-
2,2,6,6-tetramethyl-1-(1- phenyl-ethoxy)-piperidine 9 121
4,4-Bis-benzyloxy-2,2,6,6- tetramethyl-1-(1-phenyl-
ethoxy)-piperidine 10 122 2,7,7,9,9-Pentamethyl-8-(1-
phenyl-ethoxy)-1,4-dioxa-8- aza-spiro[4.5]decane 11 123
2-Ethyl-7,7,9,9-tetramethyl- 9-(1-phenyl-ethoxy)-1,4- dioxa-8-aza-
spiro[4.5]decane 12 124 7,7,9,9-Tetramethyl-8-(1-
phenyl-ethoxy)-2-propyl- 1,4-dioxa-8-aza- spiro[4.5]decane 13 125
2-Butyl-7,7,9,9-tetramethyl- 8-(1-phenyl-ethoxy)-1,4- dioxa-8-aza-
spiro[4.5]decane 14 126 7,7,9,9-Tetramethyl-2-
octyl-8-(1-phenyl-ethoxy)- 1,4-dioxa-8-aza- spiro[5.5]decane 15 127
2-Decyl-7,7,9,9- tetramethyl-8-(1-phenyl- ethoxy)-1,4-dioxa-8-aza-
spiro[4.5]decane 16 128 2-Dodecyl-7,7,9,9- tetramethyl-8-(1-phenyl-
ethoxy)-1,4-dioxy-8-aza- spiro[4.5]decane 17 129
[7,7,9,9-Tetramethyl-8-(1- phenyl-ethoxy)-1,4-dioxa-8-
aza-spiro[4.5]dec-2-yl]- methanol 18 130 Acetic acid 8-hydroxy-
7,7,9,9-tetramethyl-1,4- dioza-8-aza-spiro[4.5]dec- 2-ylmethyl
ester; compound with isopropyl-benzene 19 131 Octadecanoic acid
7,7,9,9- tetramethyl-8-(1-phenyl- ethoxy)-1,4-dioxa-8-aza-
spiro[4.5]dec-2-ylmethyl ester 20 132 Benzoic acid 7,7,9,9-
tetramethyl-8-(1-phenyl- ethoxy)-1,4-dioxa-8-aza-
spiro[4.5]dec-2-ylmethyl ester 21 133 2-Methoxymethyl-7,7,9,9-
tetramethyl-8-(1-phenyl- ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane
22 134 2-Cyclohexyloxymethyl- 7,7,9,9-tetramethyl-8-(1-
phenyl-ethoxy)-1,4-dioxa-8- aza-spiro[4.5]decane 23 135
2-Benzyloxymethyl-7,7,9,9- tetramethyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 24 136 Octanedioic acid
bis- [7,7,9,9-tetramethyl-8-(1- phenyl-ethoxy)-1,4-dioxa-- 8-
aza-spiro[4.5]dec-2- ylmethyl] ester 25 137 Terephthalic acid bis-
[7,7,9,9-tetramethyl-8-(1- phenyl-ethoxy)-1,4-dioxa-8-
aza-spiro[4.5]dec-2- ylmethyl] ester 26 138 1,4-Bis-{[7,7,9,9-
tetramethyl-8-(1-phenyl- ethoxy)-1,4-dioxa-8-aza-
spiro[4.5]dec-2-yl]- methyloxy}-butane 27 139
2,2,7,7,9,9-Hexamethyl-8- (1-phenyl-ethoxy)-1,4- dioxa-8-aza-
spiro[4.5]decane 28 140 2,3,7,7,9,9-Hexamethyl-8-
(1-phenyl-ethoxy)-1,4- dioxa-8-aza- spiro[4.5]decane 29 141
2,3-Benzo-7,7,9,9- tetramethyl-8-(1-phenyl-
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 30 142
2,3-Cyclohexano-7,7,9,9- tetramethyl-8-(1-phenyl- -
ethoxy)-1,4-dioxa-8-aza- spiro[4.5]decane 31 143
7,7,9,9-Tetramethyl-8-(1- phenyl-ethoxy)-1,4-dioxa-8-
aza-spiro[4.5]decane-2,3- dicarboxylic acid 32 144
7,7,9,9-Tetramethyl-8-(1- phenyl-ethoxy)-1,4-dioxa-8-
aza-spiro[4.5]decane-2,3- dicarboxylic acid dimethyl ester 33 145
8,8,10,10-Tetramethyl-9-(1- phenyl-ethoxy)-1,5-dioxa-9-
aza-spiro[5.5]undecane 34 146 3,3,8,8,10,10-Hexamethyl-
9-(1-phenyl-ethoxy)-1,5- dioxa-9-aza- spiro[5.5]undecane 35 147
3-Ethyl-3,8,8,10,10- pentamethyl-9-(1-phenyl-
ethoxy)-1,5-dioxa-9-aza- spiro[5.5]undecane 36 148
3,3-Diethyl-8,8,10,10- tetramethyl-9-(1-phenyl-
ethoxy)-1,5-dioxa-9-aza- spiro[5.5]undecane 37 149
3,8,8,10,10-Pentamethyl-9- (1-phenyl-ethoxy)-3-propyl-
1,5-dioxa-9-aza- spiro[5.5]undecane 38 150
3-Butyl-3-ethyl-8,8,10,10- tetramethyl-9-(1-phenyl-
ethoxy)-1,5-dioxa-9-aza- spiro[5.5]undecane 39 151
2,2,4,4-Tetramethyl-3-(1- phenyl-ethoxy)-7,16-dioxa- 3-aza-
dispiro[5.2.5.2]hexadec- -11- ene 40 152
[3,8,8,10,10-Pentamethyl-9- (1-phenyl-ethoxy)-1,5- dioxa-9-aza-
spiro[5.5]undec-3-yl]- methanol 41 153 [3-Ethyl-8,8,10,10-
tetramethyl-9-(1-phenyl- ethoxy)-1,5-dioxa-9-aza-
spiro[5.5]undec-3-yl]- methanol 42 154 Acetic acid 3,8,8,10,10-
pentamethyl-9-(1-phenyl- ethoxy)-1,5-dioxa-9-aza-
spiro[5.5]undec-3-ylmethyl ester 43 155 3-Methoxymethyl-
3,8,8,10,10-pentamethyl-9- (1-phenyl-ethoxy)-1,5- dioxa-9-aza-
spiro[5.5]undecane 44 156 3-Cyclohexyloxymethyl-
3,8,8,10,10-pentamethyl-9- (1-phenyl-ethoxy)-1,5- dioxa-9-aza-
spiro[5.5]undecane 45 157 3-Benzyloxymethyl-
3,8,8,10,10-pentamethyl-9- (1-phenyl-ethoxy)-1,5- dioxa-9-aza-
spiro[5.5]undecane 46 158 Octanedioic acid bis-
[3,8,8,10,10-pentamethyl-9- (1-phenyl-ethoxy)-1,5- dioxa-9-aza-
spiro[5.5]undec-3-ylmethyl] ester 47 159
1,6-Bis-{[3-ethyl-8,8,10,10- tetramethyl-9-(1-phenyl-
ethoxy)-1,5-dioxa-9-aza- spiro[5.5]undec-3-yl]- methyloxy}-hexane
48 160 3,8,8,10,10-Pentamethyl-9- (1-phenyl-ethoxy)-1,5-
dioxa-9-aza- spiro[5.5]undecane-3- carboxylic acid 49 161
3,8,8,10,10-Pentamethyl-9- (1-phenyl-ethoxy)-1,5- dioxa-9-aza-
spiro[5.5]undecane-3- carboxylic acid methyl ester 50 162
8,8,10,10-Tetramethyl-9- (1-phenyl-ethoxy)-1,5- dioxa-9-aza-
spiro[5.5]undecane-3,3- dicarboxylic acid diethyl ester 51 163
2,2,4,4-Tetramethyl-3-(1- phenyl-ethoxy)-7,12-dioxa-
3-aza-spiro[5.6]dodec-9- ene
[0066] Particularly preferred are the compounds of Table 1 and
2.
[0067] Most preferred are following compounds: 164
[0068]
4,4-Dibutoxy-2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperi-
dine (Table 1, No. 4) 165
[0069]
7,9-Diethyl-6,7,9-trimethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-spi-
ro[4.5]decane (Table 1, No. 10) 166
[0070]
7,9-Diethyl-2,6,7,9-tetramethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-
-spiro[4.5]decane (Table 1, No. 11) 167
[0071]
[7,9-Diethyl-6,7,9-trimethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-sp-
iro[4.5]dec-2-yl]-methanol (Table 1, No. 18) 168
[0072]
8,10-Diethyl-7,8,10-trimethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-aza-s-
piro[5.5]undecane (Table1, No. 34) 169
[0073]
8,10-Diethyl-3,3,7,8,10-pentamethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-
-aza-spiro[5.5]undecane (Table 1, No.35) 170
[0074]
2,4-Diethyl-1,2,4-trimethyl-3-(1-phenyl-ethoxy)-7,16-dioxa-3-aza-di-
spiro[5.2.5.2]hexadec-11-ene (Table 1, No. 40) 171
[0075]
[8,10-Diethyl-3,7,8,10-tetramethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9--
aza-spiro[5.5]undec-3-yl]-methanol (Table 1, No 41) 172
[0076]
9-(Cyclohex-2-enyloxy)-8,10-diethyl-3,3,7,8,10-pentamethyl-1,5-diox-
a-9-aza-spiro[5.5]undecane
[0077] Preferably the ethylenically unsaturated monomer or oligomer
is selected from the group consisting of ethylene, propylene,
n-butylene, i-butylene, styrene, substituted styrene, conjugated
dienes, acrolein, vinyl acetate, vinylpyrrolidone, vinylimidazole,
maleic anhydride, (alkyl)acrylic acidanhydrides, (alkyl)acrylic
acid salts, (alkyl)acrylic esters, (meth)acrylonitriles,
(alkyl)acrylamides, vinyl halides or vinylidene halides.
[0078] Particularly the ethylenically unsaturated monomers are
ethylene, propylene, n-butylene, i-butylene, isoprene,
1,3-butadiene, .alpha.-C.sub.5-C.sub.18alkene, styrene,
.alpha.-methyl styrene, p-methyl styrene or a compound of formula
CH.sub.2.dbd.C(R.sub.a)--(C.dbd.Z)--R.su- b.b, wherein R.sub.a is
hydrogen or C.sub.1-C.sub.4alkyl, R.sub.b is NH.sub.2,
O.sup.-(Me.sup.+), glycidyl, unsubstituted C.sub.1-C.sub.18alkoxy,
C.sub.2-C.sub.100alkoxy interrupted by at least one N and/or O
atom, 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.18alkyl)amino,
--O--CH.sub.2--CH.sub.2--N(CH.sub.3).sub.- 2 or
--O--CH.sub.2--CH.sub.2--N.sup.+H(CH.sub.3).sub.2 An.sup.-;
[0079] An.sup.- is a anion of a monovalent organic or inorganic
acid;
[0080] Me is a monovalent metal atom or the ammonium ion.
[0081] Z is oxygen or sulfur.
[0082] Examples for R.sub.a as C.sub.2-C.sub.100alkoxy interrupted
by at least one O atom are of formula 173
[0083] wherein R.sub.c is C.sub.1-C.sub.25alkyl, phenyl or phenyl
substituted by C.sub.1-C.sub.18alkyl, R.sub.d is hydrogen or methyl
and v is a number from 1 to 50. These monomers are for example
derived from non ionic surfactants by acrylation of the
corresponding alkoxylated alcohols or phenols. The repeating units
may be derived from ethylene oxide, propylene oxide or mixtures of
both.
[0084] Further examples of suitabl acrylat or methacrylat monomers
are given below. 174
[0085] An.sup.-, wherein An.sup.- and R.sub.a have the meaning as
defined above and R.sub.e is methyl or benzyl. An.sup.- is
preferably Cl.sup.-, Br.sup.- or .sup.-O.sub.3S--CH.sub.3.
[0086] Further acrylate monomers are 175
[0087] Examples for suitable monomers other than acrylates are
176
[0088] Preferably 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.4alkylamino,
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.
[0089] Particularly preferred ethylenically unsaturated monomers
are styrene, methylacrylate, ethylacrylate, butylacrylate,
isobutylacrylate, tert. butylacrylate, hydroxyethylacrylate,
hydroxypropylacrylate, dimethylaminoethylacrylate,
glycidylacrylates, methyl(meth)acrylate, ethyl(meth)acrylate,
butyl(meth)acrylate, hydroxyethyl(meth)acrylate,
hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate,
glycidyl(meth)acrylates, acrylonitrile, acrylamide, methacrylamide
or dimethylaminopropyl-methacrylamide.
[0090] Preferably the initiator compound is present in an amount of
from 0.01 mol-% to 20 mol-%, more preferably in an amount of from
0.01 mol-% to 10 mol-% and most preferred in an amount of from 0.05
mol-% to 10 mol-% based on the monomer or monomer mixture.
[0091] When monomer mixtures are used mol-% is calculated on the
average molecular weight of the mixture.
[0092] Another subject of the present 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
(co)polymerizing the monomer or monomers/oligomers in the presence
of an initiator compound of formula Ia, IIa or IIIa under reaction
conditions capable of effecting scission of the O--C bond to form
two free radicals, the radical .X being capable of initiating
polymerization.
[0093] Preferably scission of th O--C bond is eff cted by
ultrasonic treatment, heating or exposure to electromagnetic
radiation, ranging from .gamma. to microwaves.
[0094] More preferably 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.
[0095] Preferred initiators and ethylenically unsaturated monomers
have already been mentioned above.
[0096] 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.
[0097] 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%.
[0098] 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.
[0099] The aqueous polymerization reactions can be supplemented
with a water-miscible or hydrophilic cosolvent to help ensure that
the reaction mixture remains a homogeneous singl 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.
[0100] The process is particularly useful for the preparation of
block copolymers.
[0101] 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 systeme, 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 for plastics, elastomers and
adhesives.
[0102] 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. The
(co)polymers of the present invention may have a number average
molecular weight from 1 000 to 400 000 g/mol, preferably from 2 000
to 250 000 g/mol and, more preferably, from 2 000 to 200 000 g/mol.
When produced in bulk, the number average molecular weight may be
up to 500 000 (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/ionization 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.
[0103] The polymers or copolymers of the present invention have
preferably a polydispersity of from 1.0 to 2, more preferably of
from 1.1 to 1.9 and most preferably from 1.1 to 1.8.
[0104] 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.
[0105] The polymers prepared by the present invention are useful
for following applications: adhesives, det rgents, dispersants,
emulsifiers, surfactants, defoamers, adhesion promoters, corrosion
inhibitors, viscosity improvers, lubricants, rheology modifi rs,
thickeners, crosslinkers, paper treatment, water tr atment,
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.
[0106] 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.
[0107] 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.
[0108] 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.
[0109] 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.
[0110] The compounds of formula Ia, IIa and IIIa are novel. A
further subject of the present invention is therefore a compound of
formula Ia, IIa or IIIa 177
[0111] wherein
[0112] n is 1 or 2;
[0113] X is selected from the group consisting of
--CH.sub.2-phenyl, CH.sub.3CH-phenyl, (CH.sub.3).sub.2C-phenyl,
(C.sub.5-C.sub.6cycloalkyl).- sub.2CCN, 3-cyclohexenyl,
3-cyclopentenyl, (CH.sub.3).sub.2CCN, --CH.sub.2CH.dbd.CH.sub.2,
CH.sub.3CH--CH.dbd.CH.sub.2
(C.sub.1-C.sub.4alkyl)CR.sub.20--C(O)-phenyl,
(C.sub.1-C.sub.4)alkyl-CR.s- ub.20--C(O)--(C.sub.1-C.sub.4)alkoxy,
(C.sub.1-C.sub.4)alkyl-CR.sub.20--C(- O)--(C.sub.1-C.sub.4)alkyl,
(C.sub.1-C.sub.4)alkyl-CR.sub.20--C(O)--N-di(C-
.sub.1-C.sub.4)alkyl,
(C.sub.1-C.sub.4)alkyl-CR.sub.20--C(O)--NH(C.sub.1-C- .sub.4)alkyl,
(C.sub.1-C.sub.4)alkyl-CR.sub.20--C(O)--NH.sub.2, and a group of
formula 178
[0114] wherein R.sub.20 is hydrogen or (C.sub.1-C.sub.4)alkyl,
R.sub.21 is hydrogen, C.sub.1-C.sub.4alkyl or phenyl and R.sub.22
is C.sub.1-C.sub.12alkyl which is unsubstituted or substituted by
OH or N(R.sub.20)(R.sub.21) or which is interrupted by O or
NR.sub.20;
[0115] if n is 1
[0116] Y and Y' are independently C.sub.1-C.sub.12alkyl,
C.sub.3-C.sub.12alkenyl, C.sub.3-C.sub.12alkinyl,
C.sub.5-C.sub.8cycloalk- yl, phenyl, naphthyl,
C.sub.7-C.sub.9phenylalkyl; or
[0117] Y and Y' together form one of the bivalent groups
--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--,
CH(R.sub.1)--CH.sub.2--C(R.sub.2)(R- .sub.3)--,
[0118] --CH(R.sub.2)--CH2--C(R.sub.1)(R.sub.3)--,
--CH.sub.2--C(R.sub.1)(R- .sub.2)--CH(R.sub.3)--, o-phenylene,
1,2-cyclohexyliden, --CH.sub.2--CH.dbd.CH--CH.sub.2-- or 179
[0119] wherein
[0120] R.sub.1 is hydrogen, C.sub.1-C.sub.12alkyl, COOH,
COO--(C.sub.1-C.sub.12)alkyl or CH.sub.2OR.sub.4;
[0121] R.sub.2 and R.sub.3 are independently hydrogen, methyl
ethyl, COOH or COO--(C.sub.1-C.sub.12)alkyl;
[0122] R.sub.4 is hydrogen, C.sub.1-C.sub.12alkyl, benzyl, or a
monovalent acyl residue derived from an aliphatic, cycloaliphatic
or aromatic monocarboxylic acid having up to 18 carbon atoms;
[0123] if n is 2
[0124] Y and Y' together form one of the tetravalent groups 180
[0125] Q is a bisacyl residue which is derived from a
C.sub.2-C.sub.12dicarboxylic acid or C.sub.1-C.sub.12alkylene;
and
[0126] Z is C.sub.1-C.sub.12alkylene; with the proviso that
compounds A, B, C are excluded 181
[0127] The definitions and preferrences given above apply also for
the compounds.
[0128] The preparation of the compounds of the present invention is
carried out according to known reaction steps. A general method for
the preparation of the compounds of formula Ia, IIa, and IIIa
starts from the 4-oxo compounds Xa or XIa which are described in GB
2335190 or from XIIa which is a known compound described for
example in DE 2352127. 182
[0129] These starting compounds are reacted for example with
suitable monoalcohols, diols or tetrafunctional alcohols to form
intermediates of formula Xb, XIb or XIIb wherein Y, Y' and n are as
defined above. Such ketalization reactions are well known in the
art and the corresponding compounds are mostly known. The reaction
is for example described in U.S. Pat. No. 3,790,525, U.S. Pat. No.
3,899,464, U.S. Pat. No. 4,007,158 and U.S. Pat. No. 4,105,626.
183
[0130] The compounds of formula Xb, XIb and XIIb are oxidized
according to standard procedures to the corresponding nitroxides of
formula Xc, XIc and XIIc, as for xample described in GB 2335190 or
WO 99/46261. 184
[0131] The nitroxides are then coupled with a compound of formula
HX under oxidative conditions. Suitable radicals X are as defined
above. This coupling reaction is descriebed for example in GB
2335190. Preferably the coupling reaction is carried out in the
presence of a Cu(II) salt according to the method described in
International Application No. PCT/EP01/05668.
[0132] These nitroxides can also be used as polymerization
regulators in combination with a source of free radicals.
[0133] A further subject of the invention is therefore a
polymerizable composition, comprising
[0134] a) at least one ethylenically unsaturated monomer or
oligomer;
[0135] b) a compound of formula Ib or IIb 185
[0136] wherein
[0137] n is 1 or 2;
[0138] if n is 1
[0139] Y and Y' are independently C.sub.1-C.sub.12alkyl,
C.sub.3-C.sub.12alkenyl, C.sub.3-C.sub.12alkinyl,
C.sub.5-C.sub.8cycloalk- yl, phenyl, naphthyl,
C.sub.7-C.sub.9phenylalkyl; or
[0140] Y and Y' together form one of the bivalent groups
--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--,
CH(R.sub.1)--CH.sub.2--C(R.sub.2)(R- .sub.3)--,
[0141] --CH(R.sub.2)--CH.sub.2--C(R.sub.1)(R.sub.3)--,
--CH.sub.2--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--, o-phenylene,
1,2-cyclohexyliden, --CH.sub.2--CH.dbd.CH--CH.sub.2-- or 186
[0142] wherein
[0143] R.sub.1 is hydrogen, C.sub.1-C.sub.12alkyl, COOH,
COO--(C.sub.1-C.sub.12)alkyl or CH.sub.2OR.sub.4;
[0144] R.sub.2 and R.sub.3 are independently hydrogen, methyl
ethyl, COOH or COO--(C.sub.1-C.sub.12)alkyl;
[0145] R.sub.4 is hydrogen, C.sub.1-C.sub.12alkyl, benzyl, or a
monovalent acyl residue derived from an aliphatic, cycloaliphatic
or aromatic monocarboxylic acid having up to 18 carbon atoms;
[0146] if n is 2
[0147] Y and Y' together form one of the tetravalent groups 187
[0148] Q is a bisacyl residue which is derived from a
C.sub.2-C.sub.12dicarboxylic acid or C.sub.1-C.sub.12alkylene;
and
[0149] Z is C.sub.1-C.sub.12alkylene; and
[0150] c) a source of free radicals capable of initiating
polymerization of ethylenically unsaturated monomers.
[0151] Preferred is a polymerizable composition wherein in the
compound of formula Ib or IIb
[0152] n is 1
[0153] Y and Y' are independently C.sub.1-C.sub.12alkyl,
C.sub.3-C.sub.12alkenyl, ph nyl or benzyl; or
[0154] Y and Y' together form one of the bivalent groups
--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--,
CH(R.sub.1)--CH.sub.2--C(R.sub.2)(R- .sub.3)--,
--CH(R.sub.2)--CH.sub.2--C(R.sub.1)(R.sub.3)--,
--CH.sub.2--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--,
--CH.sub.2--CH.dbd.CH--CH- .sub.2-- or; wherein
[0155] R.sub.1 is hydrogen, C.sub.1-C.sub.12alkyl,
COO--(C.sub.1-C.sub.12)- alkyl or CH.sub.2OR.sub.4;
[0156] R.sub.2 and R.sub.3 are independently hydrogen, methyl
ethyl, or COO--(C.sub.1-C.sub.12)alkyl;
[0157] R.sub.4 is hydrogen, C.sub.1-C.sub.12alkyl, benzyl, or a
monovalent acyl residue derived from an aliphatic, cycloaliphatic
or aromatic monocarboxylic acid having up to 12 carbon atoms.
[0158] Specific nitroxide compounds useful in the present invention
are given in Tables 4 and 5.
4TABLE 4 Compounds according to formula (Ib) 1 188
2,6-Diethyl-4,4-dimethoxy- - 2,3,6-trimethyl-piperidin-1- oxyl 2
189 4,4-Diethoxy-2,6-diethyl- 2,3,6-trimethyl-piperidin-1- oxyl 3
190 2,6-Diethyl-2,3,6-trimethyl- 4,4-dipropoxy-piperidin-1- oxyl 4
191 4,4-Dibutoxy-2,6-diethy- l- 2,3,6-trimethyl-piperidin-1- oxyl 5
192 2,6-Diethyl-4,4- diisobutoxy-2,3,6- trimethyl-piperidin-1-oxyl
6 193 2,6-Diethyl-2,3,6-trimethyl- 4,4-bis-octyloxy-piperidin-1-
oxyl 7 194 4,4-Bis-allyoxy-2,6-diethyl-
2,3,6-trimethyl-piperidin-1- oxyl 8 195 4,4-Bis-cyclohexyl-2,6- di
thyl-2,3,6-trimethyl- piperidin-1-oxyl 9 196 4,4-Bis-benzyloxy-2,6-
diethyl-2,3,6-trimethyl- piperidin-1-oxyl 10 197
7,9-Diethyl-6,7,9-trimethyl- 1,4-dioxa-8-aza-
spiro[4.5]decan-8-oxyl 11 198 7,9-Diethyl-2,6,7,9-
tetramethyl-1,4-dioxa-8- aza-spiro[4.5]decane-8-oxyl 12 199
2,7,9-Triethyl-6,7,9- trimethyl-1,4-dioxa-8-aza-
spiro[4.5]decan-8-oxyl 13 200 7,9-Diethyl-6,7,9-trimethyl-
2-propyl-1,4-dioxa-8-aza- spiro[4.5]decan-8-oxyl 14 201
2-Butyl-7,9-diethyl-6,7,9- trimethyl-1,4-dioxa-8-aza-
spiro[4.5]decan-8-oxyl 15 202 7,9-Diethyl-6,7,9-trimethyl-
2-oxyl-1,4-dioxa-8-aza- spiro[4.5]decan-8-oxyl 16 203
2-Decyl-7,9-diethyl-6,7,9- trimethyl-1,4-dioxa-8-aza-
spiro[4.5]decan-8-oxyl 17 204 2-Dodecyl-7,9-diethyl-
6,7,9-trimethyl-1,4-dioxa- 8-aza-spiro[4.5]decan-8- oxyl 18 205
7,9-Diethyl-2- hydroxymethyl-6,7,9- trimethyl-1,4-dioxa-8-aza-
spiro[4.5]decan-8-oxyl 19 206 Acetic acid 7,9-diethyl-
6,7,9-trimethyl-1,4-dioxa-8- aza-spiro[4.5]dec-2- ylmethyl
ester-8-oxyl 20 207 Octadecanoic acid 7,9-
diethyl-6,7,9-trimethyl-1,4- dioxa-8-aza-spiro[4.5]dec- 2-ylmethyl
ester-8-oxyl 21 208 Benzoic acid 7,9-diethyl-
6,7,9-trimethyl-1,4-dioxa-8- aza-spiro[4.5]dec-2- ylmethyl
ester-8-ixyl 22 209 7,9-Diethyl-2- methoxymethyl-6,7,9-
trimethyl-1,4-dioxa-8-aza- spiro[4.5]decan-8-oxyl 23 210
2-Cyclohexyloxymethyl- 7,9-diethyl-6,7,9-trimethyl-
1,4-dioxa-8-aza- spiro[4.5]decan-8-oxyl 24 211
2-Benzyloxymethyl-7,9- diethyl-6,7,9-trimethyl-1,4- dioxa-8-aza-
spiro[4.5]decan-8-oxyl 25 212 Octanedoic acid bis-(7,9-
diethyl-8-oxyl-6,7,9- trimethyl-1,4-dioxa-8-aza-
spiro[4.5]dec-2-ylmdethyl) ester 26 213 Terephthalic acid bis-(7,9-
diethyl-8-oxyl-6,7,9- trimethyl-1,4-dioxa-8-aza-
spiro[4.5]dec-2-ylmethyl) ester 27 214 1,4-Bis-{[7,9-diethyl-6,7,9-
trimethyl-8-oxyl-1,4-dioxa- 8-aza-spiro[4.5]dec-2-yl]-
methyloxy}-butane 28 215 7,9-Diethyl-2,2,6,7,9-
pentamethyl-1,4-dioxa-8- aza-spiro[4.5]decan-8-oxyl 29 216
7,9-Diethyl-2,3,6,7,9- pentamethyl-1,4-dioxa-9-
aza-spiro[4.5]decan-8-oxyl 30 217 2,3-Benzo-7,9-diethyl-
6,7,9-trimethyl-8-oxyl-1,4- dioxa-8-aza- spiro[4.5]decane 31 218
2,3-Cyclohexano-7,8,10- trimethyl-1,5-dioxa-9-aza-
spiro[5.5]undecan-9-oxyl 32 219 7,9-Diethyl-6,7,9-trimethyl-
1,4-dioxa-8-aza- spiro[4.5]decane-2,3- dicarboxylic acid-8-oxyl 33
220 7,9-Diethyl-6,7,9-trimethyl- 1,4-dioxa-8-aza-
spiro[4.5]decane-2,3- dicarboxylic acid dimethyl ester-8-oxyl 34
221 8,10-Diethyl-7,8,10- trimethyl-1,5-dioxa-9-aza-
spiro[5.5]undecan-9-oxyl 35 222 8,10-Diethyl-3,3,7,8,10-
pentamethyl-1,5-dioxa-9- aza-spiro[5.5]undecan-9- oxyl 36 223
3,8,10-Triethyl-3,7,810- tetramethyl-1,5-dioxa-9-
aza-spiro[5.5]undecan-9- oxyl 37 224 3,3,8,10-Tetramethyl-7,8,10-
trimethyl-1,5-dioxa-9-aza- spiro[5.5]undecan-9-oxyl 38 225
8,10-Diethyl-3,7,8,10- tetramethyl-3-propyl-1,5- dioxa-9-aza-
spiro[5.5]undecan-9-oxyl 39 226 3-Butyl-3,8,10-triethyl-
7,8,10-trimethyl-1,5-dioxa- 9-aza-spiro[5.5]undecan-9- oxyl 40 227
2,4-Diethyl-1,2,4-trimethyl- 7,16-dioxa-3-aza-
dispiro[5.2.5.2]hexadec-11- en-3-oxyl 41 228 8,10-Diethyl-3-
hydroxymethyl-3,7,8,10- tetramethyl-1,5-dioxa-9-
aza-spiro[5.5]undecan-9- oxyl 42 229 3,8,10-Triethyl-3-
hydroxymethyl-7,8,10- trimethyl-1,5-dioxa-9-aza-
spiro[5.5]undecan-9-oxyl 43 230 8,10-Diethyl-3-
methoxymethyl-3,7,8,10- tetramethyl-1,5-dioxa-9-
aza-spiro[5.5]undecan-9- oxyl 44 231 3-Cyclohexyloxymethyl-
8,10-diethyl-3,7,8,10- tetramethyl-1,5-dioxa-9-
aza-spiro[5.5]undecan-9- oxyl 45 232 3-Benzyloxymethyl-8,10-
diethyl-3,7,8,10- tetramethyl-1,5-dioxa-9- aza-spiro[5.5]undecan-9-
oxyl 46 233 Acetic acid 8,10-diethyl- 3,7,8,10-tetramethyl-1,5-
dioxa-9-aza- spiro[5.5]undec-3-ylmethyl ester-9-oxyl 47 234
Octandioic acid bis- (8,10-diethyl-9-oxyl-
3,7,8,10-tetramethyl-1,5- dioxa-9-aza- spiro[5.5]undec-3- ylmethyl)
ester 48 235 1,6-Bis{3,8,10-triethyl- 7,8,10-trimethyl-9-oxyl-1,5-
dioxa-9- azaspiro[5.5]undec-3- methyloxy}-hexane 49 236
8,10-Diethyl-3,7,8,10- tetramethyl-1,5-dioxa-9-
aza-spiro[5.5]undecane-3- carboxylic acid-9-oxyl 50 237
8,10-Diethyl-3,7,8,10- tetramethyl-1,5-dioxa-9-
aza-spiro[5.5]undecane-3- carboxylic acid methyl ester-9-oxyl 51
238 8,10-Diethyl-7,8,10- trimethyl-1,5-dioxa-9-aza-
spiro[5.5]undecane-3,3- dicarboxylic acid diethyl ester-9-oxyl 52
239 3,3-Bisspiro-{8,10-diethyl- 7,8,10-trimethyl-9-oxyl- -1,5-
dioxa-9-aza- spiro[5.5]undecane} 53 240
2,4-Diethyl-1,2,4-trimethyl- 7,12-dioxa-3-aza-
spiro[5.6]dodec-9-en-3- oxyl 54 241 Acetic acid 3,8,10-triethyl-
7,8,10-trimethyl-1,5-dioxa- 9-aza-spiro[5.5]undec-3-yl- methyl
ester-9-oxyl 55 242 Octadecanoic acid 3,8,10-
triethyl-7,8,10-trimethyl-1,5- dioxa-9-aza-spiro[5.5]un-
dec-3-ylmethyl ester-9-oxyl
[0159]
5TABLE 5 Compounds according to formula (IIb) 1 243
2,2-Diethyl-4,4-dimethox- y- 6,6-dimethyl-piperidin-1- oxyl 2 244
4,4-Diethoxy-2,2-diethyl- 6,6-dimethyl-piperidin-1- oxyl 3 245
2,2-Diethyl-6,6-dimethyl-4,4- dipropoxy-piperidin-1-oxyl 4 246
4,4-Dibutoxy-2,2-diethyl- 6,6-dimethyl-piperidin-1- oxyl 5 247
2,2-Diethyl-4,4-diisobutoxy- 6,6-dimethyl-piperidin-1- oxyl 6 248
2,2-Diethyl-6,6-dimethyl-4,4- - bis-octyloxy-piperidin-1-oxyl 7 249
4,4-Bis-allyloxy-2,2-diethyl- 6,6-dimethyl-piperidin-1- oxyl 8 250
4,4-Bis-cyclohexyloxy-2,2- diethyl-6,6-dimethyl- piperidin-1-oxyl 9
251 4,4-Bis-benzyloxy-2,2- diethyl-6,6-dimethyl- piperidin-1-oxyl
10 252 7,7-Diethyl-9,9-dimethyl- 1,4-dioxa-8-aza-
spiro[4.5]decan-8-oxyl 11 253 7,7-Diethyl-2,9,9-trimethyl-
1,4-dioxa-8-aza- spiro[4.5]decan-8-oxyl 12 254
2,7,7-Triethyl-9,9-dimethyl- 1,4-dioxa-8-aza-
spiro[4.5]decan-8-oxyl 13 255 7,7-Diethyl-9,9-dimethyl-2-
propyl-1,4-dioxa-8-aza- spiro[4.5]decan-8-oxyl 14 256
2-Butyl-7,7-diethyl-9,9- dimethyl-1,4-dioxa-8-aza-
spiro[4.5]decan-8-oxyl 15 257 7,7-Diethyl-9,9-dimethyl-2-
octyl-1,4-dioxa-8-aza- spiro[4.5]decan-8-oxyl 16 258
2-Decyl-7,7-diethyl-9,9- dimethyl-1,4-dioxa-8-aza-
spiro[4.5]decan-8-oxyl 17 259 2-Dodecyl-7,7-diethyl-9,9-
dimethyl-1,4-dioxa-8-aza- spiro[4.5]decan-8-oxyl 18 260
7,7-Diethyl-2-hydroxymethyl- 9,9-dimethyl-1,4-dioxa-8-aza-
spiro[4.5]decan-8-oxyl 19 261 Acetic acid 7,7-diethyl-9,9-
dimethyl-1,4-dioxa-8-aza- spiro[4.5]dec-2-ylmethyl ester-8-oxyl 20
262 Octadecanoic acid 7,7- diethyl-9,9-dimethyl-1,4-
dioxa-8-aza-spiro[4.5]dec- 2-ylmethyl ester-8-oxyl 21 263 Benzoic
acid 7,7-diethyl-9,9- dimethyl-1,4-dioxa-8-aza-
spiro[4.5]dec-2-ylmethyl ester-8-oxyl 22 264 7,7-Diethyl-2-
methoxymethyl-9,9- dimethyl-1,4-dioxa-8-aza- spiro[4.5]decan-8-oxyl
23 265 2-Cyclohexyloxymethyl-7,7- diethyl-9,9-dimethyl-1,4-
dioxa-8-aza- spiro[4.5]decan-8-oxyl 24 266 2-Benzyloxymethyl-7,7-
diethyl-9,9-dimethyl-1,4- dioxa-8-aza-spiro[4.5]decan- 8-oxyl 25
267 Octanedioic acid bis(7,7- diethyl-8-oxyl-9,9-dimethyl-
1,4-dioxa-8-aza- spiro[4.5]dec-2-ylmethyl)_ ester 26 268
Terephthalic acid bis-(7,7- diethyl-8-oxyl-9,9-dimethyl-
1,4-dioxa-8-aza- spiro[4.5]dec-2-ylmethyl) ester 27 269
1,4-Bis-{[7,7-diethyl-9,9- dimethyl-8-oxyl-1,4-dioxa-8-
aza-spiro[4.5]dec-2-yl]- methyloxy}-butane 28 270
7,7-Diethyl-2,2,9,9- tetramethyl-1,4-dioxa-8- -
aza-spiro[4.5]decan-8-oxyl 29 271 7,7-Diethyl-2,3,9,9-
tetramethyl-1,4-dioxa-8- aza-spiro[4.5]decan-8-oxyl 30 272
2,3-Benzo-7,7-diethyl-9,9- dimethyl-8-oxyl-1,4-dioxa-8-
aza-spiro[4.5]decane 31 273 2,3-Cyanohexano-7,7-
diethyl-9,9-dimethyl-8-oxyl- 1,4-dioxa-8-azaspiro [4.5]decane 32
274 7,7-Diethyl-9,9-dimethyl- 1,4-dioxa-8-aza-
spiro[4.5]decane-2,3- dicarboxylic acid-8-oxyl 33 275
7,7-Diethyl-9,9-dimethyl-1,4- dioxa-8-aza- spiro[4.5]decane-2,3-
dicarboxylic acid dimethyl ester-8-oxyl 34 276
8,8-Diethyl-10,10-dimethyl- 1,5-dioxa-9-aza-
spiro[5.5]undecan-9-oxyl 35 277 8,8-Diethyl-3,3,10,10-
tetramethyl-1,5-dioxa-9- aza-spiro[5.5]undecan-9- oxyl 36 278
3,8,8-Triethyl-3,10,10- trimethyl-1,5-dioxa-9-aza-
spiro[5.5]undecane-9-oxyl 37 279 3,3,8,8-Tetraethyl-10,10-
dimethyl-1,5-dioxa-9-aza- spiro[5.5]undecan-9-oxyl 38 280
8,8-Diethyl-3,10,10- trimethyl-3-propyl-1,5- dioxa-9-aza-
spiro[5.5]undecan-9-oxyl 39 281 3-Butyl-3,8,8-triethyl-10,10-
dimethyl-1,5-dioxa-9-aza- spiro[5.5]undecan-9-oxyl 40 282
2,2-Diethyl-4,4-dimethyl- 7,16-dioxa-3-aza-
dispiro[5.2.5.2]hexadec-11- en-3-oxyl 41 283 8,8-Diethyl-3-
hydroxymethyl-3,10,10- trimethyl-1,5-dioxa-9-aza-
spiro[5.5]undecan-9-oxyl 42 284 3,8,8-Triethyl-3-
hydroxymethyl-10,10- dimethyl-1,5-dioxa-9-aza-
spiro[5.5]undecan-9-oxyl 43 285 8,8-Diethyl-3-
methoxymethyl-3,10,10- trimethyl-1,5-dioxa-9-aza-
spiro[5.5]undecan-9-oxyl 44 286 3-Cyclohexyloxymethyl-8,8-
diethyl-3,10,10-trimethyl- 1,5-dioxa-9-aza-
spiro[5.5]undecan-9-oxyl 45 287 3-Benzyloxymethyl-8,8-
diethyl-3,10,10-trimethyl- -1,5- dioxa-9-aza-
spiro[5.5]undecan-9-oxyl 46 288 Acetic acid 8,8-diethyl-
3,10,10-trimethyl-1,5-dioxa- 9-aza-spiro[5.5]undec-3- ylmethyl
ester-9-oxyl 47 289 Octanedioic acids bis-(8,8-
diethyl-9-oxyl-3,10,10- trimethyl-1,5-dioxa-9-aza-
spiro[5.5]undec-3-ylmethyl) ester 48 290
1,6-Bis{[3,8,8-triethyl-10,- 10- dimethyl-9-oxyl-1,5-dioxa-9-
aza-spiro[5.5]undec-3-yl]- - methyloxy}-hexane 49 291
8,8-Diethyl-3,10,10- trimethyl-1,5-dioxa-9-aza-
spiro[5.5]undecane-3- carboxylic acid-9-oxyl 50 292
8,8-Diethyl-3,10,10- trimethyl-1,5-dioxa-9-a- za-
spiro[5.5]undecane-3- carboxylic acid methyl ester-9-oxyl 51 293
8,8-Diethyl-10,10-dimethyl- 1,5-dioxa-9-aza-
spiro[5.5]undecane-3,3- dicarboxylic acid diethyl ester-9-oxyl 52
294 3,3-Bisspiro{8,8-diethyl- 10,10-dimethyl-9-oxyl-1,5-
dioxa-9-aza- spiro[5.5]undecane} 53 295 2,2-Diethyl-4,4-dimethyl-
7,12-dioxa-3-aza- spiro[5.6]dodec-9-en-3-oxyl
[0160] The compounds of Table 4, and 5 are particularly
preferred.
[0161] Most preferred are the following compounds. 296
[0162] 4,4-Dibutoxy-2,6-diethyl-2,3,6-trimethyl-piperidin-1-oxyl
(Tab. 4, No.4) 297
[0163]
7,9-Diethyl-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxyl
(Tab.4, No.10) 298
[0164]
7,9-Diethyl-2,6,7,9-tetramethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-o-
xyl (Tab.4, No. 11) 299
[0165]
7,9-Diethyl-2-hydroxymethyl-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4-
.5]decan-8-oxyl (Tab.4, No.18) 300
[0166]
8,10-Diethyl-7,8,10-trimethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-o-
xyl (Tab. 4, No. 34) 301
[0167]
8,10-Diethyl-3,3,7,8,10pentamethyl-1,5-dioxa-9-aza-spiro[5.5]undeca-
n-9-oxyl (Tab. 4, No. 35) 302
[0168]
2,4-Diethyl-1,2,4-trimethyl-7,16-dioxa-3-aza-dispiro[5.2.5.2]hexade-
c-11-en-3-oxyl (Tab. 4, No. 40) 303
[0169]
8,10-Diethyl-3-hydroxymethyl-3,7,8,10-tetramethyl-1,5-dioxa-9-aza-s-
piro[5.5]undecan-9-oxyl (Tab. 4, No.41)
[0170] The source of radicals may be a bis-azo compound, a peroxide
or a hydroperoxide.
[0171] 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.
[0172] Preferably, the source of radicals is
2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methyl-butyronitrile),
2,2'-azobis(2,4-dimethylvaleronitril- e),
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.
[0173] Preferred peroxides and hydroperoxides are acetyl
cyclohexane sulphonyl peroxide, diisopropyl peroxy dicarbonate,
t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl
perpivalate, t-amylperpivalate, bis(2,4-dichlorobenzoyl)peroxide,
diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide,
dilauroyl peroxide, bis (2-methylbenzoyl) peroxide, disuccinic acid
peroxide, diacetyl peroxide, dibenzoyl peroxide, t-butyl per
2-ethylhexanoate, bis-(4-chlorobenzoyl)-peroxide, t-butyl
perisobutyrate, t-butyl permaleinate,
1,1-bis(t-butylperoxy)3,5,5-trimethylcyclohexane,
1,1-bis(t-butylperoxy)cyclohexane, t-butyl peroxy isopropyl
carbonate, t-butyl perisononaoate, 2,5-dimethylhexane
2,5-dibenzoate, t-butyl peracetate, t-amyl perbenzoate, t-butyl
perbenzoate, 2,2-bis (t-butylperoxy) butane, 2,2 bis
(t-butylperoxy) propane, dicumyl peroxide,
2,5-dimethylhexane-2,5-di-t-butylperoxide, 3-t-butylperoxy
3-phenylphthalide, di-t-amyl peroxide,
.alpha.,.alpha.'-bis(t-butylperoxy isopropyl) benzene, 3,5-bis
(t-butylperoxy)3,5-dimethyl 1,2-dioxolane, di-t-butyl peroxide,
2,5-dimethylhexyne-2,5-di-t-butylperoxide, 3,3,6,6,9,9-hexamethyl
1,2,4,5-tetraoxa cyclononane, p-menthane hydroperoxide, pinane
hydroperoxide, diisopropylbenzene mono-.alpha.-hydroperoxide,
cumene hydroperoxide or t-butyl hydroperoxide.
[0174] These compounds are commercially available.
[0175] If more than one radical source is used, a mixture of
substitution patterns is obtainable.
[0176] The radical source is preferably present in an amount of
from 0.01 mol-% to 30 mol-%, more preferred in an amount of from
0.1 mol-% to 20 mol-% and most preferred in an amount of from 0.5
mol-% to 10 mol-% based on the monomer or monomer mixture.
[0177] Preferably the nitroxyl compound is present in an amount of
from 0.01 mol-% to 20 mol-%, more preferably in an amount of from
0.01 mol-% to 10 mol-% and most preferred in an amount of from 0.05
mol-% to 10 mol-% based on the monomer or monomer mixture.
[0178] The molar ratio of the radical source to the compound of
formulae Ib, IIb or IIIb may be from 1:10 to 10:1, preferably from
1:5 to 5:1 and more preferably from 1:2 to 2:1.
[0179] Still another subject of the present invention is a process
for preparing an oligomer, a cooligomer, a polymer or a copolymer
(block or random) by free radical polymerization of at l ast one
ethylenically unsaturated monomer/oligomer, which comprises
subjecting the above composition to heat or actinic radiation.
[0180] The composition is preferably subjected to heat from
90.degree. C. to 160.degree. C.
[0181] A further subject of the invention is a compound of formula
Ib or IIb 304
[0182] wherein
[0183] n is 1 or 2;
[0184] if n is 1
[0185] Y and Y' are independently C.sub.1-C.sub.12alkyl,
C.sub.3-C.sub.12alkenyl, C.sub.3-C.sub.12alkinyl,
C.sub.5-C.sub.8cycloalk- yl, phenyl, naphthyl,
C.sub.7-C.sub.9phenylalkyl; or
[0186] Y and Y' together form one of the bivalent groups
--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--,
CH(R.sub.1)--CH.sub.2--C(R.sub.2)(R- .sub.3)--,
--CH(R.sub.2)--CH.sub.2--C(R.sub.1)(R.sub.3)--,
--CH.sub.2--C(R.sub.1)(R.sub.2)--CH(R.sub.3)--, o-phenylene,
1,2-cyclohexyliden, --CH.sub.2--CH.dbd.CH--CH.sub.2-- or 305
[0187] wherein
[0188] R.sub.1 is hydrogen, C.sub.1-C.sub.12alkyl, COOH,
COO--(C.sub.1-C.sub.12)alkyl or CH.sub.2OR.sub.4;
[0189] R.sub.2 and R.sub.3 are independently hydrogen, methyl
ethyl, COOH or COO--(C.sub.1-C.sub.12)alkyl;
[0190] R.sub.4 is hydrogen, C.sub.1-C.sub.12alkyl, benzyl, or a
monovalent acyl residue derived from an aliphatic, cycloaliphatic
or aromatic monocarboxylic acid having up to 18 carbon atoms;
[0191] if n is 2
[0192] Y and Y' together form one of the tetravalent groups 306
[0193] Q is a bisacyl residue which is derived from a
C.sub.2-C.sub.12dicarboxylic acid or C.sub.1-C.sub.12alkylene;
and
[0194] Z is C.sub.1-C.sub.12alkylene; with the proviso that
compounds D, E, F, G, H 307
[0195] are excluded.
[0196] Yet another subject of the invention is a polymer or
oligomer, having attached at least one oxyamine group derived from
formula Ia, IIa or IIIa.
[0197] The polymers or oligomers can also be termed
macroinitiators. They can be used to start polymerization for
example with a second monomer which then results in the formation
of a block copolym r as already described above.
[0198] Further subjects of the invention are the use of a compound
of formulae Ia, IIa or IIIa for the polymerization of ethylenically
unsaturated monomers and the use of a compound of formulae Ib or
IIb together with a source of free radicals for the polymerization
of an ethylenically unsaturated monomer.
[0199] Definitions and preferences for the various substituents
have already been mentioned. They apply also for the other subjects
of the invention including the preferences and the individual
compounds.
[0200] The following examples illustrate the invention.
EXAMPLE A1
[0201]
7,9-diethyl-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxyl
(Table 4, Compound 10) 308
[0202] The compound is prepared according to U.S. Pat. No.
4,105,626 (example 5).
EXAMPLE A2
[0203]
7,9-diethyl-2-hydroxymethyl-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4-
.5]decan-8-oxyl (Table 4, Compound 18) 309
[0204] The title compound is prepared by oxidising
7,9-diethyl-2-hydroxyme-
thyl-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4.5]decan, prepared
according to U.S. Pat. No. 4,105,626. A red oil is obtained.
Elemental analysis for C.sub.15H.sub.28NO.sub.4 calculated: C,
62.91%; H, 9.85%; N, 4.89%; found: C, 62.83%; H, 9.83%; N,
4.75%.
EXAMPLE A3
[0205]
8,10-diethyl-3,3,7,8,10-pentamethyl-1,5-dioxa-9-aza-spiro[5.5]undec-
an-9-oxyl (Tabelle 2, Compound 35) 310
[0206] The title compound is prepared by oxidising
7,9-diethyl-2-hydroxyme-
thyl-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4.5]decan, prepared
according to U.S. Pat. No. 4,105,626. A red oil is obtained.
Elemental analysis for C.sub.15H.sub.28NO.sub.4 calculated: C,
68.42%; H, 10.81; N, 4.69; found: C, 68.21%; H, 10.66%; N,
4.63%.
EXAMPLE A4
[0207]
7,9-diethyl-6,7,9-trimethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-spi-
ro[4.5]decane (Table 1, Compound 10) 311
[0208] To a solution of 10.3 g (0.04 mol)
7,9-diethyl-6,7,9-trimethyl-1,4--
dioxa-8-aza-spiro[4.5]decan-8-oxyl (Table 2, compound 10) in 40 ml
ethylbenzene 8.3 ml (0.06 mol) 70% t-butyl-hydroperoxide in water
and 0.7 ml of a catalyst solution (containing 13.44 g CuCl.sub.2
and 4.24 g LiCl in 153 ml ethanol) are added. The mixture is
stirred at 65.degree. C. until it is colorless (approximately 90
minutes). After cooling to room temperature 25 ml water and 5 g
Na.sub.2S.sub.2O.sub.5 are added and the mixture is vigorously
stirred for 10 minutes. The organic phase is separated, washed with
H.sub.2O and the remaining ethylbenzene is evaporated. The residue
chromatographically purified (SiO.sub.2 hexane-ethylacetate (19:1))
and 10.3 g of the title compound is obtained as colorless oil.
Elemental analysis for C.sub.22H.sub.35NO.sub.3 calculated: C,
73.09%; H, 9.76%; N, 3.87%; found: C, 72.95%; H, 9.79%; N,
3.68%.
EXAMPLE A5
[0209]
[7,9-diethyl-6,7,9-trimethyl-8-(1-phenyl-ethoxy)-1,4-dioxa-8-aza-sp-
iro[4.5]dec-2-yl]-methanol (Table 1, Compound 18) 312
[0210] The title compound is prepared in analogy to exampla A4 from
7,9-diethyl-2-hydroxymethyl-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4.5]dec-
an-8-oxyl (Table 4, compound 18). Colorless oil,
.sup.1H-NMR(CDCl.sub.3, 300 MHz, d ppm): 7.4-7.1 m, (5 ArH),
4.7-4.55 m (1H), 4.3-3.55 m (5H), 2.1-0.5 m (26H).
EXAMPLE A6
[0211]
8,10-diethyl-3,3,7,8,10-pentamethyl-9-(1-phenyl-ethoxy)-1,5-dioxa-9-
-aza-spiro[5.5]undecane (Table 1, Compound 35) 313
[0212] The title compound is prepared in analogy to example A4 from
8,10-diethyl-3,3,7,8,10-pentamethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-o-
xyl (Table 4, compound 35). Colorless oil. Elemental analysis for
C.sub.25H.sub.41NO.sub.3 calculated: C, 74.40%; H, 10.24%; N,
3.47%; found: C, 74.19%; H, 10.43%; N, 3.43%.
EXAMPLE A7
[0213]
3,8,10-triethyl-3-hydroxymethyl-7,8,10-trimethyl-1,5-dioxa-9-aza-sp-
iro[5.5]undecan-9-oxyl (Table 4, Compound 42) 314
[0214] The title compound is prepared in analogy to Example A1 by
oxidizing
(3,8,10-triethyl-7,8,10-trimethyl-1,5-dioxa-9-aza-spiro[5.5]und-
ec-3-yl)-methanol (prepared as described in U.S. Pat. No.
4,105,626) as a red oil. GC-MS: narrow bundle of 4 peaks
(diastereomers) with M.sup.+=328
(C.sub.18H.sub.34NO.sub.4=328.48).
EXAMPLE A8
[0215] Acetic Acid
3,8,10-triethyl-7,8,10-trimethyl-1,5-dioxa-9-aza-spiro[-
5.5]undec-3-yl-methyl ester-9-oxyl (Table 4, Compound 54) 315
[0216] The title compound is prepared in analogy to Exampl A1 by
oxidizing acetic acid
3,8,10-triethyl-7,8,10-trimethyl-1,5-dioxa-9-aza-spiro[5.5]un-
dec-3-yl-methyl ester (prepared in analogy to U.S. Pat. No.
4,105,626, Example 4) as a red oil.
EXAMPLE A9
[0217] Octadecanoic Acid
3,8,10-triethyl-7,8,10-trimethyl-1,5-dioxa-9-aza--
spiro[5.5]undec-3-ylmethyl ester-9-oxyl (Table 4, Compound 55).
316
[0218] The title compound is prepared in analogy to Example 1 by
oxidizing octadecanoic acid
3,8,10-triethyl-7,8,10-trimethyl-1,5-dioxa-9-aza-spiro[-
5.5]undec-3-yl-methyl ester (prepared in analogy to U.S. Pat. No.
4,105,626, Example 4) as a red oil. MS (Cl): MH.sup.+=595
(C.sub.36H.sub.88NO.sub.5=594.95).
EXAMPLE A10
[0219] Acetic Acid
7,9-diethyl-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4.5]d-
ec-2-yl-methyl ester-8-oxyl (Table 4, Compound 19) 317
[0220] The title compound is prepared in analogy to Example A1 by
oxidizing acetic acid
7,9-diethyl-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4-
.5]dec-2-yl-methyl ester (prepared as described in U.S. Pat. No.
4,105,626, Example 4) as a red oil. GC-MS: narrow bundle of 6 peaks
(diastereomers) with M.sup.+=328
(C.sub.17H.sub.30NO.sub.5=328.43).
EXAMPLE A11
[0221]
2-(8,10-diethyl-3,3,7,8,10-pentamethyl-1,5-dioxa-9-aza-spiro[5.5]un-
dec-9-yloxy)-propionic acid 2-hydroxy-ethyl ester (Table 1,
Compound 54) 318
[0222] To a stirred mixture of 89.54 g (0.3 mol)
8,10-diethyl-3,3,7,8,10-p-
entamethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl (Tab. 4, Nr.
35), 43.04 (0.3 mol) copper (I) bromide, 19.06 (0.3 mol) copper
powder and 103.9 g (0.6 mol) pentamethyl-ethylene-triamine in 500
ml toluene are added dropwis within 30 minutes and under nitrogen
59.1 g (0.3 mol) 2-bromopropionic acid-2-hydroxyethylester. The
mixture is stirred at rt for 17 h and then filtered. The filtrate
is washed with water (3.times.500 ml) and th n with a solution of
EDTA (300 ml, 1%). The organic layer is dried over Na.sub.2SO.sub.4
and then evaporated to afford 122.8 g (98.5%) of the title compound
as a slightly yellow oil.
[0223] .sup.1H-NMR(CDCl.sub.3, 300 MHz, d ppm): 4.45-4.26 m, (1H),
4.25-4.23 m (2H), 3.85 bs m (2H), 3.71-0.72 (36H).
[0224] B) Polymerizations with n-butylacrylate Using Compounds of
Formulae Ia, IIa or IIIa as Initiators/Regulators
[0225] General Remarks:
[0226] Solvents and monomers are distilled over a Vigreux column
under argon atmosphere or under vacuum, shortly before being
used.
[0227] 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.
[0228] At the start of the polymerization reaction, all starting
materials are homogeneously dissolved.
[0229] 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.
[0230] Characterization of the polymers is carried out by MALDI-MS
(Matrix Assisted Laser Desorption Ionization Mass Spectrometry)
and/or GPC (Gel Permeation Chromatography).
[0231] 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.
[0232] GPC: Is performed using RHEOS 4000 of FLUX INSTRUMENTS.
Tetrahydrofurane (THF) is us d as a solvent and is pumped at 1
ml/min. Two chromatography columns ar 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 2 000 000 Dalton.
Detection is carried out using a RI-Detector ERC-7515A of ERCATECH
AG at 30.degree. C.
EXAMPLE B1
[0233] Polymerization of n-butylacrylate with Compound 10, Table 1
(Example A4) at 145.degree. C.
[0234] In a 50 ml three neck flask, equipped with thermometer,
cooler and magnetic stirrer, 644 mg (1.78 mmol) of compound 10,
Table 1 and 15 g (117 mmol) of n-butylacrylate are mixed and
degased. The clear solution obtained is heated under argon to
145.degree. C. and polymerization is carried out during 5 h. The
reaction mixture is then cooled to 60.degree. C. The remaining
monomer is removed by evaporation under high vacuum. 11.1 g (74%)
of the initial monomer have reacted. A clear yellow viscous fluid
is obtained.
[0235] Mn=6460, Mw=8280, PD=1.28
EXAMPLE B2
[0236] Polymerization of n-butylacrylate with Compound 35, Table 1
(Example A6) at 145.degree. C.
[0237] In a 50 ml three neck flask, equipped with thermometer,
cooler and magnetic stirrer, 718 mg (1.78 mmol) of compound 35,
Table 1 and 15 g (117 mmol) of n-butylacrylate are mixed and
degased. The clear solution obtained is heated under argon to
145.degree. C. and polymerization is carried out during 5 h. The
reaction mixture is then cooled to 60.degree. C. The remaining
monomer is removed by evaporation under high vacuum. 12.3 g (82%)
of the initial monomer have reacted. A clear yellow viscous fluid
is obtained.
[0238] Mn=6630, Mw=8450, PD=1.27
EXAMPLE B3
[0239] Polymerization of n-butylacrylate with Compound 18, Table 1
(Example A5) at 145.degree. C.
[0240] In a 50 ml three neck flask, equipped with thermometer,
cooler and magnetic stirrer, 679 mg (1.78 mmol) of compound 18,
Table 1 and 15 g (117 mmol) of n-butylacrylate are mixed and
degased. The clear solution obtained is heated under argon to
145.degree. C. and polymerization is carried out during 5 h. The
reaction mixture is then cooled to 60.degree. C. The remaining
monomer is removed by evaporation under high vacuum. 12.37 g
(82.5%) of the initial monomer have reacted. A clear yellow viscous
fluid is obtained.
[0241] Mn=7000, Mw=9000, PD=1.29
EXAMPLE B4
[0242] Preparation of a Block Copolym r from n-butylacrylat and
N,N-dim thylaminoethylacrylat (DMAEA) Using Compound 10, Table
1
[0243] 1) Preparation of Poly-n-butylacrylate
[0244] In a 50 ml three neck flask, equipped with thermometer,
cooler and magnetic stirrer, 644 mg (1.78 mmol) of compound 10,
Table 1 and 15 g (117 mmol) of n-butylacrylate are mixed and
degased. The clear solution obtained is heated under argon to
145.degree. C. and polymerization is carried out during 5 h. The
reaction mixture is then cooled to 60.degree. C. The remaining
monomer is removed by evaporation under high vacuum. 11.1 g (74%)
of the initial monomer have reacted. A yellow viscous fluid is
obtained.
[0245] Mn=5700, Mw=8050, PD=1.41
[0246] 2) Preparation of a Block Copolymer with DMAEA
[0247] In a 50 ml three neck flask, equipped with thermometer,
cooler and magnetic stirrer, 6.5 g of the above
poly(n-butylacrylate and 6.5 g (45.5 mmol)
N,N-dimethylaminoethylacrylate are mixed and degased. The clear
solution obtained is heated under argon to 145.degree. C. and
polymerization is carried out during 3 h. The reaction mixture is
then cooled to 70.degree. C. The remaining monomer is removed by
evaporation under high vacuum. 1. g (15%) of the monomer have
reacted. A yellow/brownish viscous fluid is obtained.
[0248] Composition (NMR): 87 weight-% butylacrylat/13 weight-%
N,N-dimethylaminoethylacrylat Mn=5700, Mw=8170, PD=1.43
EXAMPLE B5
[0249] Preparation of a Block Copolymer from n-butylacrylat and
N,N-dimethyl-aminoethylacrylat (DMAEA) Using Compound 35, Table
1
[0250] 1) Preparation of Poly-n-butylacrylate
[0251] In a 50 ml three neck flask, equipped with thermometer,
cooler and magnetic stirrer, 718 mg (1.78 mmol) of compound 35,
Table 1 and 15 g (117 mmol) of n-butylacrylate are mixed and
degased. The clear solution obtained is heated under argon to
145.degree. C. and polymerization is carried out during 5 h. The
reaction mixture is then cooled to 60.degree. C. The remaining
monomer is removed by evaporation under high vacuum. 12.3 g (82%)
of the initial monomer have reacted. A clear yellow viscous fluid
is obtained.
[0252] Mn=6170, Mw=8300, PD=1.34
[0253] 2) Preparation of a Block Copolymer with DMAEA
[0254] In a 50 ml three neck flask, equipped with thermometer,
cooler and magnetic stirrer, 6.5 g of the above
poly(n-butylacrylate and 5 g (35 mmol)
N,N-dimethylaminoethylacrylate are mixed and degased. The clear
solution obtained is heated under argon to 145.degree. C. and
polymerization is carried out during 3 h. The reaction mixture is
then cooled to 70.degree. C. The remaining monomer is removed by
evaporation under high vacuum. 1. g (22%) of the monomer have
reacted. A yellow/brownish viscous fluid is obtained.
[0255] Composition (NMR): 82 weight-% butylacrylat/18 weight-%
N,N-dimethylaminoethylacrylat Mn=5700, Mw=8350, PD=1.46
[0256] C) Polymerizations with Styrene Using Compounds of Formulae
Ia, IIa or IIIa as Initiators/Regulators
[0257] In an evacuated Schlenk tube, flushed with Argon and
equipped with magnetic stirrer, the amount of nitroxylether given
in Table 6 is added to 50 mol freshly distilled n-styrene under an
Argon atmosphere. The Schlenk tube is closed and the remaining
oxygen is removed in two freeze thaw cycles with liquid nitrogen.
The tube is filled with Argon and heated to the temperatures given
in Table 6 for 6 hours with stirring. The remaining monomer is
removed under vacuum at room temperature. Drying is continued until
constant weight of the residue. Molecular weight and distribution
are determined using gel permeation chromatography with
tetrahydrofurane and calibrated with polystyrene standards. The
results are given in Table 6.
6TABLE 6 Temp Amount of Conversion M.sub.n M.sub.w Exp. No.
(.degree. C.) regulator (%) (GPC) (GPC) M.sub.w/M.sub.n C0 130 1
mol % 82 7600 9500 1.24 C1 130 0.1 mol % 81 42700 62800 1.47 C2 120
1 mol % 165 6200 7400 1.19 C3 120 0.1 mol % 55 35000 47900 1.37 C4
110 1 mol % 40 3800 4700 1.25 C5 110 0.1 mol % 28 22700 28300 1.26
C6 100 1 mol % 20 1700 2800 1.65 C7 100 0.1 mol % 15 13100 17800
1.36
[0258] 1 mol % corresponds to 8.72.times.10.sup.-2 mol NOR/I styr
ne, 0.1 mol % corresponds to 8.72.times.10.sup.-3 mol NOR/I
styrene.
[0259] Initiator/regulator is compound 35, Table 1 319
[0260] Polymerizations with Styrene Using Compounds of Formulae Ib,
IIb and Dibenzoylperoxide (BPO) as Regulators/Initiators
[0261] In an evacuated Schlenk tube, flushed with argon and
equipped with magnetic stirrer, the amount of nitroxyl and BPO
given in Table 7 is added to 50 mol freshly distilled n-styrene
under an argon atmosphere. The Schlenk tube is closed and the
remaining oxygen is removed in two freeze thaw cycles with liquid
nitrogen. The tube is filled with argon and heated to the
temperatures given in Table 7 for 6 hours with stirring. The
remaining monomer is removed under vacuum at room temperature.
Drying is continued until constant weight of the residue. Molecular
weight and distribution are determined using gel permeation
chromatography with tetrahydrofurane and calibrated with
polystyrene standards. The results are given in Table 7.
7TABLE 7 Exp. Temp Concen- Yield M.sub.n M.sub.n M.sub.w M.sub.w/
No. (.degree. C.) trations (%) (calc) (GPC) (GPC) M.sub.n C8 130
[NO.multidot.] = 44 5100 5300 6600 1.24 8.72 .times. 10.sup.-2
mol/l [BPO] = 6.7 .times. 10.sup.-2 mol/l C9 130 [NO.multidot.] =
47 5300 5400 7100 1.32 8.72 .times. 10.sup.-2 mol/l [BPO] = 6.7
.times. 10.sup.-2 mol/l C10 130 [NO.multidot.] = 77 81000 39000
55900 1.43 8.72 .times. 10.sup.-3 mol/l [BPO] = 6.7 .times.
10.sup.-3 mol/l C11 120 [NO.multidot.] = 43 45500 29400 38900 1.33
8.72 .times. 10.sup.-3 mol/l [BPO] = 6.7 .times. 10.sup.-3 mol/l
[BPO] = 6.7 .times. 10.sup.-3 mol/l corresponds 0.077 mol %
Initiator, [BPO] = 6.7 .times. 10.sup.-2 mol/l corresponds 0.77 mol
% Initiator [NO.multidot.] = 8.72 .times. 10.sup.-3 mol/l
corresponds 0.1 mol % NO Radical, [NO.multidot.] = 8.72 .times.
10.sup.-2 mol/l corresponds 1 mol % NO Radical
[0262] The NO radical is compound 35, Table 4: 320
[0263] D. Blockcopolymerizations
[0264] 20 grams of a styrene macroinitiator obtained by
polymerizing styrene at 120.degree. C. following the procedure as
described in section C with a concentration of 0.05 mol % of
compound 35 (Table 1) (molecular weight data see table) are
dissolved in a glass autoclave in 1) 100 g styrene, 2) a mixture of
90 g of styrene and 30 g of acrylonitrile.
[0265] The solutions are degassed by argon purge for 30 minutes and
subsequently heated in an oil bath at 110.degree. C. for 6 hours.
The polymer is obtained by precipitation into a 10 fold excess of
methanol and dried in vacuo to remove unreacted monomer until
constant weight. Molecular weights were determined by GPC as
described in section C. The shift in molecular weight from D 0 to
experiments D1 und D2 (Table 8) clearly indicates the formation of
a block copolymer and confirms the capability of reinitiation of
polymers synthesized using the instant compounds.
8TABLE 8 Yield of added Exp. # Comonomer(s) monomer(s) (%) M.sub.n
M.sub.w M.sub.w/M.sub.n D 0 60400 108600 1.80 D 1 Styrene 45 96700
165600 1.71 D 2 Sty/AN 50 143900 258700 1.80
* * * * *