Polymerization process for ionic monomers

Details Polymerization process for ionic monomers Polymerization process for ionic monomers

2001-10-05

2003-09-23

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...

C526S091000, C526S240000, C526S310000, C526S328000

Reexamination Certificate

active

06624262

ABSTRACT:

FIELD OF INVENTION
The invention is directed towards controlled polymerization processes for monomers bearing ionic substituents and for preparation of block copolymers, including water soluble block copolymers. More specifically, the invention is directed towards extending and improving the utility of controlled or living radical (co)polymerization processes by disclosing the parameters and requirements for the controlled polymerization of radically (co)polymerizable monomers from initiators bearing additional functionality and provides for the direct production of polymers bearing ionic substituents by the direct (co)polymerization of monomers comprising ionic substituents, particularly in the presence of water.
BACKGROUND OF THE INVENTION
There is a continuing effort in polymer chemistry to develop new polymerization processes and new polymers. A relatively recent development in polymer chemistry has been the development of controlled or living polymerization processes. A controlled or living polymerization process is one in which chain transfer and termination reaction are essentially nonexistent relative to the polymer propagation reaction. These developments have led to the production of polymers that exhibit macro functionality and to the development of functional polymers that possess specific chemical reactivity. The new polymers extend the level of control available to materials engineers in processing polymers and using polymers as building blocks in, or components for, subsequent material forming reactions, such as copolymerizations, chain extensions and crosslinking reactions, and interaction with substrates, including dispersed solids.
A significant economic hurdle which continually needs to be overcome in this effort is to provide the benefits of controlled polymerization from available low cost monomers in available commercial process equipment. These long term objectives have provided the backdrop, or driving force, for the continuing advances in controlled polymerization of radically (co)polymerizable monomers, disclosed in earlier patent applications, and provide the incentive to extend, simplify and make more robust the process known as atom transfer radical polymerization (ATRPo).
The recently developed ATRP process and polymers developed from the classic ATRP reaction are described in U.S. patent application Ser. No. 09/018,554, now U.S. Pat. No. 6,538,091 and 09/534,827, the entire contents of which are hereby incorporated herein by reference. Methods for exercising control over many parameters in a catalytic process for the controlled polymerization of a wide range of free radically (co)polymerizable monomers have been described in publications authored or co-authored by Krzysztof Matyjaszewski and others. See for example, Wang, J. S. and Matyjaszewsk, K.,
J. Am. Chem. Soc., vol.
117, p.5614 (1995); Wang, J. S. and Matyjaszewsk, K.,
Macromolecules,
vol. 28, p. 7901 (1995); K. Matyjaszewski et al.,
Science,
vol. 272, p.866 (1996); K. Matyjaszewski et al., “Zerovalent Metals in Controlled/”living” Radical Polymerization,” Macromolecules, vol. 30, pp. 7348-7350 (1997); J. Xia and K. Matyjaszewski, “Controlled/“Living” Radical Polymerization. Homogenous Reverse Atom Transfer Radical Polymerization Using AIBN as the Initiator,”
Macromolecules,
vol. 30, pp. 7692-7696 (1997); U.S. patent application Ser. No. 09/126,768, now U.S. Pat. No. 6,121,371, the entire contents of which are hereby incorporated by reference; U.S. Pat. Nos. 5,807,937, 5,789,487, 5,910,549, 5,763,548, 5,789,489, 5,945,491, 6,111,022, 6,121,371, 6,124,411 and 6,162,882, and U.S. patent application Ser. No. 09/034,187, U.S. Pat. No. 6,407,187, Ser. No. 09/018,554, U.S. Pat. No. 6,538,091, Ser. No. 09/431,871, U.S. Pat. No. 6,162,882, Ser. Nos. 09/359,359, 09/359,591, U.S. Pat. No. 6,512,060, Ser. No. 09/369,157, U.S. Pat. No. 6,541,580, Ser. No. 09/126,768, U.S. Pat. No. 6,121,371, and Ser. No. 09/534,827, the entire contents of each are hereby incorporated herein by reference. The subtle interactions between the parameters have been further explored and implementation of the teachings disclosed in these publications has allowed the preparation of many inherently useful novel materials displaying control over functionality and topology, and production of novel tele-functional building blocks for further material forming reactions, resulting from application of the site specific functional and topological control attainable through this robust controlled polymerization process for free radically (co)polymerizable monomers.
The system or process employed to gain control over the polymerization of free radically (co)polymerizable monomers has been described in earlier applications as comprising the use of four components: (i) an initiator molecule; (ii) a transition metal compound having (iii) an added or associated counterion and the transition metal compound complexed with (iv) a ligand(s). The initiator molecule, or polymerization originator molecule may be any molecule comprising one or more radically transferable atom(s) or group(s) capable of participating in a reversible redox reaction with the transition metal compound. The transition metal compound may include an added or associated counterion and comprise a transition metal salt. So that all reactive oxidation states are soluble to some extent in the reaction medium, the transition metal may be complexed with the ligand(s). The components of the system may be optimized to provide more precise control for the (co)polymerization of the free radically polymerizable monomers. See U.S. Pat. No. 5,763,548, the entire contents of which are hereby incorporated herein by reference.
In an embodiment known as “reverse” ATRP, the initiator molecule described above can be formed in-situ by reaction of a free radical with the redox conjugate of the transition metal compound. Other components of the polymerization system such as the choice of the radically transferable atom or group, counterion initially present on the transition metal, and optional solvent may influence the process. U.S. Pat. No. 5,807,937 provides as an example of a single molecule containing a combination of functions, a complex in which the counterion and ligand components are in one molecule. The role of a deactivator, the “persistent radical,” or for ATRP, the transition metal redox conjugate, is also described in U.S. Pat. No. 5,807,937.
While not to be limited to the following description, the theory behind ATRP disclosed in the previous work is that polymerization proceeds essentially by cleavage (and preferably essentially homolytic cleavage) of the radically transferable atom or group from the initiator molecule or, during the polymerization process the dormant polymer chain end, by a reversible redox reaction with a complexed transition metal catalyst, without any strong carbon-transition (C-Mt) bond formation between the active growing polymer chain end and the transition metal complex. Within this theory as the transition metal complex, in a lower active oxidation state, or in its activator state, activates the initiator or dormant polymer chain end by homolytically removing the radically transferable atom or group from the initiating molecule, or growing polymer chain end, in a reversible redox reaction, an active species is formed that allows other chemistry, essentially free radical based chemistry to be conducted. The transition metal complex in the higher oxidation state, the redox conjugate state or deactivator state, transfers a radically transferable atom or group to the active initiator molecule or growing chain end, thereby reforming the lower oxidation state transition metal complex. When free radical based chemistry occurs, a new molecule comprising a radically transferable atom or group is also formed. In prior publications, the catalytically active transition metal compound, which can be formed in situ or added as a preformed complex, has been described as containing a range of counterions. The counterion(s) may be the same as the radically trans

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