2,2,6,6 diethyl-dimethyl-1-alkoxy-piperidine compounds and...

Details 2,2,6,6 diethyl-dimethyl-1-alkoxy-piperidine compounds and... 2,2,6,6 diethyl-dimethyl-1-alkoxy-piperidine compounds and...

2001-03-19

2003-09-23

Dentz, Bernard (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C546S205000, C546S208000, C546S222000, C546S224000, C546S242000, C546S244000

Reexamination Certificate

active

06624306

ABSTRACT:

The present invention relates to selected 1-alkoxy-2,2 diethyl-6,6 dimethyl piperidine and 1-alkoxy-2,6 diethyl-2,3,6 trimethyl piperidine derivatives which are substituted in the 4 position by an oxygen or nitrogen atom; 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 diethyl-6,6 dimethyl piperidine and 1-alkoxy-2,6 diethyl-2,3,6 trimethyl piperidine derivatives which are substituted in the 4 position by an oxygen or nitrogen atom 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.
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.
U.S. Pat. No, 4,581,429 to Solomon et al., issued Apr. 8, 1986, discloses a free radical polymerization process which controls the growth of polymer chains to produce short chain or oligomeric homopolymers and copolymers, including block and graft copolymers. The process employs an initiator having the formula (in part) R′R″N—O—X, where X is a free radical species capable of polymerizing unsaturated monomers. The reactions typically have low conversion rates. Specifically mentioned radical R′R″N—O. 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.
Recently other attempts to develop new polymerization regulators have been published. WO 98/4408 and WO 98/30601 disclose heterocyclic compounds suitable for controlled polymerization processes. WO 98/13392 discloses open chain alkoxyamines which are derived from NO gas or from nitroso compounds.
GB 2335190 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.
It has now been found, that amongst those 2,2,6,6-tetraalkylpiperidines generically disclosed in GB 2335190 those are of particular value which are derivatives of 1-alkoxy-2,2 diethyl-6,6 dimethyl piperidine and of 1-alkoxy-2,6 diethyl-2,3,6 trimethyl piperidine and which are substituted in the 4 position by an oxygen or nitrogen atom, which itself is further substituted.
The steric hindrance introduced by the two diethyl groups leads to an optimized balance in terms of stability of the compounds, initiating activity and control of polymerization.
The particular substitution pattern in 2 and 6 position of the piperidine 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° C.
The compounds exhibit an unchanged initiating/regulating activity even after storage at elevated temperatures as for example used in conventional stability tests.
The oxygen or nitrogen atom in the 4 position of the piperidine ring allows a variety of substitutions. This may for example be used to adjust secondary properties such as the compound's polarity and hence its compatibility with the monomer, oligomer and polymer mixture or also its volatility.
One subject of the present invention is a compound according to formula Ia or IIa
wherein
Y is a radical
 R
1
is hydrogen, —COOH, —COO(C
1
-C
4
alkyl), —COO-phenyl, —COObenzyl, C
1
-C
8
alkoxy, C
1
-C
18
alkyl, C
2
-C
4
alkenyl, C
1
-C
18
alkyl or C
2
-C
4
alkenyl substituted by OH, —COOH, —COO(C
1
-C
4
)alkyl, C
2
-C
18
alkyl which may be interrupted by one or more oxygen atom, unsubstituted cyclopentyl, cyclohexyl, cyclohexenyl, phenyl or naphthyl; or cyclopentyl, cyclohexyl, cylohexenyl, phenyl or naphthyl which are substituted by C
1
-C
4
alkyl, —COOH or —COO—(C
1
-C
4
alkyl)
R
2
is hydrogen, C
1
-C
18
alkyl or R
1
and R
2
together with the nitrogen atom form a 5-membered ring which may have an unsaturated bond or be fused to a benzene ring; R
3
is hydrogen or C
1
-C
18
alkyl; and
X is selected from the group consisting of —(C
5
-C
12
)-3-cycloalkenyl, —CH
2
-phenyl, CH
3
CH-phenyl, (CH
3
)
2
C-phenyl, (C
5
-C
6
cycloalkyl)
2
CCN, (CH
3
)
2
CCN, —CH
2
CH═CH
2
, CH
3
CH—CH═CH
2
(C
1
-C
4
alkyl)CR
20
—C(O)-phenyl, (C
1
-C
4
)alkyl-CR
20
—C(O)—(C
1
-C
4
)alkoxy, (C
1
-C
4
)alkyl-CR
20
—C(O)—(C
1
-C
4
)alkyl, (C
1
-C
4
)alkyl-CR
20
—C(O)—N-di(C
1
-C
4
)alkyl, (C
1
-C
4
)alkyl-CR
20
—C(O)—NH(C
1
-C
4
)alkyl, (C
1
-C
4
)alkyl-CR
20
—C(O)—NH
2
, wherein R
20
is hydrogen or (C
1
-C
4
)alkyl; with the proviso that benzoic acid 2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidin-4-yl ester is excluded.
C
1
-C
18
alkyl 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, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.
Examples of C
2
-C
18
alkyl interrupted by —O— are for example 3-oxapentane, 4-oxaheptane, 3,6-dioxaoctane, 4,7-dioxadecane, 4,9-dioxadodecane, 3,6,9-trioxaundecane and 4,7,10-trioxatridecane.
Alkyl substituted by a group —COOH is for example CH
2
—COOH, CH
2
—CH
2
—COOH, (CH
2
)
3
—COOH or CH
2
—CHCOOH—CH
2
—CH
3
Examples of alkoxy containing not more than 8 carbon atoms are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy or octoxy.
C
2
-C
4
alkenyl is for example ethenyl, propenyl or butenyl; preferably ethenyl or —C(CH
3
)═CH
2
.
Cyclohexyl substituted by COOH is for example cyclohexane-carbonic acid. Phenyl substituted by COOH is for example benzoic acid. Phenyl substituted by C
1
-C
4
alkyl is for example toluene or xylene.
Preferably X is —CH
2
-phenyl, CH
3
CH-phenyl,
(3-cyclohexenyl) or (CH
3
)
2
C-phenyl.
More preferably X is CH
3
CH-phenyl.
Preferred compounds are of formulae Ia or IIa wherein Y is a radical of formula
and R
1
has the meaning as defined above.
Particularly preferred are the following individual compounds.
Compounds according to formula (Ia).
Formic acid 2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidin-4-yl ester;
Acetic acid 2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidin-4-yl ester;
Propionic acid 2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidin-4-yl ester;
Butyric acid 2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidin-4-yl ester;
Pentanoic acid 2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidin-4-yl ester;
Hexanoic acid 2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidin-4-yl ester;
Heptanoic acid 2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidin-4-yl ester;
Octanoic acid 2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidin-4-yl ester;
Nonanoic acid 2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidin-4-yl ester;
Decanoic acid 2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidin-4-yl ester;
Undecanoic acid 2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidin-4-yl ester;
Dodecanoic acid 2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidin-4-yl ester;
Tridecanoic acid 2,6-diethyl-

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