Nitroxyl derivatives with glycidyl or alkylcarbonyl groups...

Details Nitroxyl derivatives with glycidyl or alkylcarbonyl groups... Nitroxyl derivatives with glycidyl or alkylcarbonyl groups...

2000-09-05

2003-05-20

Wu, David W. (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S217000, C526S346000, C526S329200, C526S318400, C526S335000, C526S340400, C526S303100, C564S001000

Reexamination Certificate

active

06566468

ABSTRACT:

The present invention relates to glycidyl or alkylcarbonyl functional nitroxyle derivatives, a polymerizable composition comprising a) at least one ethylenically unsaturated monomer and b) a glycidyl or alkylcarbonyl functional nitroxide initiator compound. Further aspects of the present invention are a process for polymerizing ethylenically unsaturated monomers, the use of glycidyl or alkylcarbonyl functional nitroxide initiators for radical polymerization.
More specifically, in one of its aspects the present invention relates to polymerizable compositions and polymerization processes which provide polymeric resin products having low polydispersity, which polymerization processes proceed with good monomer to polymer conversion efficiencies. In particular, this invention relates to stable free radical-mediated polymerization processes which provide homopolymers, random copolymers, block copolymers, multiblock copolymers, graft copolymers and the like, at enhanced rates of polymerization and enhanced monomer to polymer conversions. The polymers produced by the present invention contain a glycidyl or alkylcarbonyl group attached to the starting molecule of the radical chain reaction.
Polymers or copolymers prepared by free radical polymerization processes inherently have broad molecular weight distributions or polydispersities which are generally higher than about four. One reason for this is that most of the free radical initiators have half lives that are relatively long, ranging from several minutes to many hours, and thus the polymeric chains are not all initiated at the same time and the initiators provide growing chains of various lengths at any time during the polymerization process. Another reason is that the propagating chains in a free radical process can react with each other in processes known as combination and disproportionation, both of which are irreversibly chain-terminating reaction processes. In doing so, chains of varying lengths are terminated at different times during the reaction process, resulting in resins consisting of polymeric chains which vary widely in length from very small to very large and which thus have broad polydispersities. If a free radical polymerization process is to be used for producing narrow molecular weight distributions, then all polymer chains must be initiated at about the same time and termination of the growing polymer-chains by combination or disproportionation processes must be avoided.
Conventional radical polymerization reaction processes pose various significant problems, such as difficulties in predicting or controlling the molecular weight, the polydispersity and the modality of the polymers produced. These prior art polymerization processes produce polymers having broad polydispersities and in some instances, low polymerization rates. Furthermore, free radical polymerization processes in bulk of the prior art are difficult to control because the polymerization reaction is strongly exothermic and an efficient heat removal in the highly viscous polymer is mostly impossible. The exothermic nature of the prior art free radical polymerization processes often severely restricts the concentration of reactants or the reactor size upon scale-up. In case that additional functional groups, such as glycidyl groups are present in one of the monomers, these may be transformed into undesired groups under such reaction conditions.
Due to the above mentioned uncontrollable polymerization reactions, gel formation in conventional free radical polymerization processes are also possible and cause broad molecular weight distributions and/or difficulties during filtering, drying and manipulating the product resin.
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 R′R″N—O. radical groups are derived from tetraethylisoindoline, tetrapropylisoindoline, tetramethylpiperidine, tetramethylpyrrolidine or di-t-butylamine.
The radical initiators, polymerization processes and resin products of the present invention have an additional glycidyl or alkylcarbonyl group, which can be used for further reactions. The resulting resins are useful in many applications.
The glycidyl or alkylcarbonyl group of the present initiators remainsessentially unchanged during the radical polymerization reaction. Therefore the radical initiators of the present invention offer the possibility, after the radical polymerizabon is accomplished or stopped, to react the glycidyl group of the oligomers or polymers in a second step with nucleophiles such as alcohols, mercaptanes, amines, metal organic compounds or the like, thereby changing the properties of the oligomers or polymers.
The glycidyl group of the initiators can also be reacted in a first step for example by anionic polymerization in the presence of for example dicyandiamide, butyl-Lithium or other strong bases leading to oligomeric/polymeric radical initiators.
S. Kobatake et al, Macromolecules 1997, 30, 4238-4242 and in WO 97/36894 disclose the anionic polymerization of butadiene in the presence of compound (a) which contains a glycidyl group in a side chain. This compound acts as a terminating reagent for the anionic polymerization of butadiene.
The resulting macromolecule can be further used as a macroinitiator for radical polymerization and for preparing block copolymers containing a poylbutadiene segment.
The present invention provides initiators for radical polymerization which contain the glycidyl or alkylcarbonyl group attached directly or separated by a spacer group to the aryl group. The initiators show a high reactivity, good rates of polymerization and good monomer to polymer conversions.
The remaining glycidyl or alkylcarbonyl group is highly reactive towards nucleophiles and can readily be transformed into other chemical groups i desired.
The compounds of the present invention are also useful as terminating agents in the anionic polymerization of for example butadiene as described in WO 97136894.
The polymerization processes and resin products of the present invention are useful in many applications, including a variety of specialty applications, such as for the preparation of block copolymers which are useful as compatibilizing agents for polymer blends or dispersing agents for coating systems or for the preparation of narrow molecular weight resins or oligomers for use in coating technologies and thermoplastic films or as toner resins and liquid immersion development ink resins or ink additives used for electrophotographic imaging processes.
Surprisingly, it has been found that it is possible to produce polymers or copolymers of narrow polydispersity and a high monomer to polymer conversion even at relative low temperatures and at short reaction times, leaving the glycidyl group essentially unchanged. The resulting polymers/copolymers are of high purity and in many cases colorless, therefore not requiring any further purification.
One subject of the present invention is to provide new initiators of formula (Ia) or (Ib)
wherein the R
1
, are each independently of one another hydrogen, halogen, NO
2
, cyano,
—CONR
5
R
6
, —(R
9
)COOR
4
, —C(O)—R
7
, —OR
8
, —SR
8
, —NHR
8
, —N(R
8
)
2
, carbamoyl, di(C
1
-C
18
alkyl)carbamoyl,
—C(═NR
5
)(NHR
6
); unsubstituted C
1
-C
18
alkyl, C
2
-C
18
alkenyl, C
2
-C
18
alkynyl, C
7
-C
9
phenylalkyl, C
3
-C
12
cycloalkyl or
C
2
-C
12
heterocycloalkyl; or
C
1
-C
18
alkyl, C
2
-C
18
alkenyl, C
2
-C
18
alkynyl, C
7
-C
9
phenylalkyl, C
3
-C
12
cycloalkyl or C
2
-C
12
heterocycloalkyl, which are substituted by NO
2
, halogen, amino, hydroxy, cyano, carboxy, C
1
-C
4
alkoxy, C
1
-C
4
alkylthio, C
1
-C
4
alkylamino

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