Polymeric stabilizers having low polydispersity

Details Polymeric stabilizers having low polydispersity Polymeric stabilizers having low polydispersity

2001-06-21

2003-06-24

Zalukaeva, Tatyana (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S213000, C526S217000, C526S220000, C526S318400, C526S263000, C526S262000, C526S259000, C526S265000, C546S186000

Reexamination Certificate

active

06583245

ABSTRACT:

The present invention relates to radically polymerizable compositions, containing at least one light stabilizer with an ethylenically unsaturated group and to oligomers, polymers, cooligomers or copolymers having low polydispersity M
w
/M
n
, which are prepared by controlled radical polymerization from the polymerizable composition. Further aspects of the invention are a process for their preparation, their use as light or heat stabilizers for organic materials, particularly for synthetic polymers, paints, enamels or varnishes and the organic materials thus stabilized.
The stabilization of polymers with light/heat stabilizers such as 2,2,6,6-tetramethylpiperidine derivatives, hydroxy-benzophenones, hydroxy-benzotriazoles and hydroxy-phenyl-s-triazines is well known. It is also known to prepare and to use oligomeric or polymeric light stabilizers of the above mentioned classes for the stabilization of polymers. This is for example described in U.S. Pat. No. 4,294,949 and in U.S. Pat. No. 4,785,063. These polymeric light stabilizers are all prepared by a conventional free radical polymerization process.
However polymers or copolymers prepared by free radical polymerization processes inherently have broad molecular weight distributions or polydispersities which are generally higher than about four. One reason for this is that most of the free radical initiators have half lives that are relatively long, ranging from several minutes to many hours, and thus the polymeric chains are not all initiated at the same time and the initiators provide growing chains of various lengths at any time during the polymerization process.
Due to the broad molecular weight distribution and high molecular weights of the polymeric light stabilizers problems arise when they are incorporated into paints, coatings, or thermoplastic polymers. They cause for example a strong viscosity increase in paints and coatings, which is undesirable for the paint's application, in particular for the spray application of automotive coatings. In thermoplastic polymers compatibility problems may arise particularly with the high molecular weight portion of the polymeric light stabilizers. For these reasons polymeric light stabilizers having a low polydispersity are desirable for many applications.
The light stabilizers of the present invention are polymeric resin products having low polydispersity. The polymerization process proceeds with good monomer to polymer conversion efficiency, thus being also feasible on an industrial scale. In particular, this invention relates to stable free radical-mediated polymerization processes or to a, free radical initiated polymerization process by the ATRP (Atom Transfer Radical Polymerization) method which provide homopolymers, alternate-, gradient- or random copolymers, block copolymers or multiblock copolymers of different classes of light stabilizers.
The so made polymers or copolymers are highly compatible with thermoplastic polymers and thermosetting coatings. They are very efficient light/heat stabilizers either when used alone or in combination with other known stabilizers. Due to their low polydispersity they are easy to incorporate into other polymers, without for example significantly increasing their viscosity or melting properties.
One subject of the present invention is a polymerizable composition, comprising a) at least one compound of formula (I)
(RG)—A—(Stab)  (I),
wherein
(Stab) is a light stabilizer radical selected from the group consisting of sterically hindered amines, hydroxyphenyl-s-triazines, hydroxyphenyl-benzotriazols and o-hydroxy-benzophenones; A is a spacer group or a direct bond; and
(RG) is a group containing at least one ethylenically unsaturated functional group; and either b1) a compound of formula (II)
Y—X  (II),
 wherein
X represents a group having at least one carbon atom and is such that the free radical derived from X is capable of initiating polymerization and
Y represents a group being such that the free radical Y· derived from it forms a stable free radical; or b2) a stable free radical Y· and a free radical source from which a radical is formed capable of initiating polymerization; or b3) a compound of formula (III)
 and a catalytically effective amount of an oxidizable transition metal complex catalyst, wherein
p represents a number greater than zero and defines the number of initiator fragments;
q represents a number greater than zero;
[In] represents a radically transferable atom or group capable of initiating polymerization and -[Hal] represents a leaving group; and optionally c) one or more ethylenically unsaturated monomers or oligomers different from those of formula (I).
The sterically hindered amines are preferably selected from the class of piperidines, piperazinones, piperazindiones or morpholinones.
Preferably component a) of formula (I) is a compound of formulae (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii) or (Ij)
W is O, or NR
110
;
A is a direct bond, —(C
2
-C
12
)alkylene-W—, —(C
3
-C
12
)alkenylene-W—, —CH
2
—HC(OH)—CH
2
—W—, —(C
3
-C
12
)alkinylene-W—, (C
5
-C
12
)cycloalkylene-W—, —(C
2
-C
12
)alkylene-W— interrupted by at least one oxygen or nitrogen atom or a group —CH
2
—CHR
110
—W—, a group —CHR
111
—COOP wherein P is —(CH
2
—HCR
112
)
n
— or a group —CH
2
—HC(OH)—CH
2
—, wherein R
110
, R
111
, R
112
and n are as defined below;
R
110
is H or methyl R
102
is hydrogen, OH, C
1
-C
18
alkyl, C
3
-C
8
alkenyl, C
3
-C
8
alkynyl; C
7
-C
12
aralkyl, C
1
-C
18
alkanoyl, C
3
-C
18
alkenoyl, C
1
-C
18
alkanoyloxy, glycidyl, C
1
-C
18
alkoxy, C
5
-C
12
cycloalkyl, C
5
-C
12
cycloalkoxy or a group —CH
2
CHR
110
(OH);
R
103
is H, OH, NH
2
, C
1
-C
18
alkoxy, C
1
-C
18
alkanoyloxy, C
6
-C
18
aryloyloxy, C
1
-C
18
alkanoylamino, C
1
-C
18
alkylamino, C
1
-C
18
alkylamino, benzyloxy or together with the linking carbon atom forms a C
5
-C
6
cycloalkyl radical or a C
5
-C
6
heterocycloalkyl radical containing one or two oxygen or nitrogen atoms;
R
104
, R
105
, R
106
, R
107
are independently C
1
-C
8
alkyl or C
5
-C
12
cyloalkyl, or R
104
and R
105
and/or R
106
and R
107
together with the carbon atom to which they are attached form-a C
5
-C
12
cycloalkyl group;
R
108
and R
109
independently are H, C
1
-C
8
alkyl or phenyl;
R
110
is hydrogen, C
1
-C
18
alkyl or phenyl;
R
111
is hydrogen or C
1
-C
12
alkyl;
R
112
is hydrogen or methyl;
R
201
and R
202
are independently H, OH, CN, C
1
-C
18
alkyl, C
1
-C
18
alkoxy, halogen, C
1
-C
18
alkanoyl, C
1
-C
18
alkanoyloxy, C
1
-C
18
alkanoylamino, or phenyl which is unsubstituted or substituted with halogen, OH, CN, NO
2
, C
1
-C
18
alkyl, C
1
-C
18
alkoxy or a group —O—CH
2
—HC(OH)—CH
2
—OR
206
;
R
203
and R
204
are independently H, OH, CN, C
1
-C
18
alkyl, C
1
-C
18
alkoxy, halogen, C
1
-C
18
alkanoyl, C
1
-C
18
alkanoyloxy, C
1
-C
18
alkanoylamino, or phenyl which is unsubstituted or substituted with halogen, OH, CN, NO
2
, C
1
-C
18
alkyl, C
1
-C
18
alkoxy or a group —O—CH
2
—HC(OH)—CH
2
—OR
206
with the proviso that at least one of both is OH;
R
205
is H, halogen, phenyl, C
1
-C
18
alkyl, C
5
-C
12
cycloalkyl, C
7
-C
12
aralkyl or a group —SR
208
, —SO
2
R
208
, —COOR
208
or PO(OR
208
)
2
;
R
206
is C
1
-C
18
alkyl, C
3
-C
18
alkyl interrupted by at least one oxygen atom, phenyl which is unsubstituted or substituted with halogen, OH, CN, NO
2
, C
1
-C
18
alkyl, C
1
-C
18
alkoxy, C
5
-C
6
cycloalkyl which is unsubstituted or substituted by C
1
-C
4
alkyl or a group —C(O)R
207
;
R
207
C
1
-C
18
alkyl or phenyl which is unsubstituted or substituted with halogen, OH, CN, NO
2
, C
1
-C
18
alkyl or C
1
-C
18
alkoxy;
R
208
is C
1
-C
18
alkyl, C
5
-C
6
cycloalkyl or phenyl;
R
209
is H, halogen, phenyl, C
1
-C
18
alkyl, C
5
-C
12
cycloalkyl, C
7
-C
12
aralkyl or a group —SR
208
, —SO
2
R
208
, —COOR
208
or PO(OR
208
)
2
;
n is a number from 0 to 12, and
k is a number from 0 to 12.
Preferably R
108
and R
109
are hydrogen and the other substituents are as defined above.
Preferably R
104
, R
105
, R
106
and R
10

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