Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Compositions to be polymerized by wave energy wherein said...
Reexamination Certificate
2001-01-29
2003-02-11
Berman, Susan W. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Compositions to be polymerized by wave energy wherein said...
C522S018000, C522S039000, C522S065000, C522S170000, C522S175000, C522S177000, C522S182000, C522S188000, C526S220000, C526S217000, C526S328000, C526S328500, C526S329200, C526S329300, C526S341000, C526S346000, C564S300000, C564S301000
Reexamination Certificate
active
06518326
ABSTRACT:
The present invention relates to open chain alkoxyamine compounds, a polymerizable composition comprising a) at least one ethylenically unsaturated monomer and b) at least one open chain alkoxyamine compound. Further aspects of the present invention are a process for polymerizing ethylenically unsaturated monomers, and the use of open chain alkoxyamine compounds for controlled polymerization. The intermediate N-oxyl derivatives, a composition of the N-oxyl derivatives with ethylenically unsaturated monomers and a free radical initiator X., 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 enhanced 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.
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. 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.
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 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.
EP-A-735 052 discloses a method for preparing thermoplastic polymers of narrow poly-dispersities by free radical-initated polymerization, which comprises adding a free radical initiator and a stable free radical agent to the monomer compound.
This method has the disadvantage that uncontrollable recombinations of initiator radicals occur immediately after their formation, thus producing variable ratios between initiator radicals and stable free radicals. Consequently there is no good control of the polymerization process.
There is therefore still a need for polymerization processes for the preparation of narrow polydispersity polymeric resins with defined molecular weights using the economical free radical polymerization techniques. These polymerization processes will also control the physical properties of the polymers such as viscosity, hardness, gel content, processability, clarity, high gloss, durability, and the like.
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 now been found that it is possible to overcome the afore mentioned shortcomings of the prior art by providing a polymerizable composition containing specific initiator compounds. Polymerization of the composition results in a polymer or copolymer of narrow polydispersity and a high monomer to polymer conversion even at relatively low temperatures and at short reaction times, making the polymerization process particularly suitable for industrial applications. The resulting copolymers are of high purity and in many cases colorless, therefore not requiring any further purification.
The present invention relates to open chain alkoxyamine compounds which have no or at most only one electron withdrawing group at the C-atom in &agr;-position to the nitrogen atom. These compounds are stable enough at low temperature and decompose readily at elevated temperature. Therefore being almost ideally suitable for controlled polymerizations.
One object of the present invention is a compound according to formula Ia, Ib or Ic
wherein
Y is O or CH
2
;
Q is O or NR
20
, wherein R
20
is hydrogen or C
1
-C
18
alkyl;
R
1
is tertiary C
4
-C
18
alkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR
21
or C(O)—R
22
wherein R
21
is hydrogen, a alkali metal atom or C
1
-C
18
alkyl and R
22
is C
1
-C
18
alkyl; or
R
1
is C
5
-C
12
cycloalkyl, C
5
-C
12
cycloalkyl which is interrupted by at least one O or N atom, a polycyclic alkyl radical or a polycyclic alkyl radical which is interrupted by at least one O or N atom;
R
2
and R
3
are independently C
1
-C
18
alkyl, benzyl, C
5
-C
12
cycloalkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR
21
or C(O)—R
22
or together with the carbon atom form a C
5
-C
12
cycloalkyl ring;
if Y is O,
R
4
and R
12
are OH, O(alkali-metal) C
1
-C
18
alkoxy, benzyloxy, NR
23
R
24
, wherein R
23
and R
24
are independently from each other hydrogen, C
1
-C
18
alkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR
21
or C(O)—R
22
;
if Y is CH
2
,
R
4
is OH, C
1
-C
18
alkoxy, benzyloxy, O—C(O)—(C
1
-C
18
)alkyl or NR
23
R
24
;
R
12
is a group C(O)R
25
, wherein R
25
is OH, C
1
-C
18
alkoxy, benzyloxy, NR
23
R
24
, wherein R
23
and R
24
are independently from each other hydrogen, C
1
-C
18
alkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR
21
or C(O)—
Kramer Andreas
Lazzari Dario
Nesvadba Peter
Zink Marie-Odile
Berman Susan W.
Ciba Specialty Chemicals Corporation
Stevenson Tyler A.
LandOfFree
Open chain alkoxyamine compounds and their use as... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Open chain alkoxyamine compounds and their use as..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Open chain alkoxyamine compounds and their use as... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3173453