Stable free radical polymerization mechanism

A free-radical polymerization mechanism can be excluded on the basis of the polymer microstructure and experiments with radical inhibitors. Rhodium(I)-spe-cies, formed by reduction of Rh " salts used as catalyst precursors by butadiene monomer, have been suggested as the active species. The catalyst is stable during the aqueous polymerization for over 30 h [23]. Catalyst activities are moderate with up to ca. 2x10 TO h [24, 25]. By contrast to industrially important free-radical copolymerization, styrene is not incorporated in the rhodium-catalyzed butadiene polymerization [26]. Only scarce data is available regarding the stability and other properties of the polymer dispersions obtained. Precipitation of considerable portions of the polymer has been mentioned at high conversions in butadiene polymerization [23, 27]. 

Fig. 2. The mechanisms of (1) stable free radical polymerizations, (2) reversible redox polymerizations (i.e., ATRP), and (3) degenerative chain transfer...

Matyjaszewski et al. systematically investigated the effect of electron donors (ED), such as pyridine and triethylamine, on the CRP of VAc with Co(acac)2. They proposed that the polymerization mechanism of VAc with Co(acac)2 in the absence of electron donor was a degenerative transfer process as shown in scheme 3(a). The polymerization in the presence of electron donor was a stable free radical polymerization controlled by the reversible homolytic cleavage of cobalt(III) dormant species as shown in scheme 3 (b). ... 

Random copolymers of styrene/isoprene and styrene/acrylonitrile have been prepared by stable free radical polymerization. By varying the comonomer mole fractions over the range 0.1-0.9 in low conversion SFRP reactions it has been demonstrated that the incorporation of the two monomers in the copolymer is analogous to that found in conventional free radical copolymerizations. The composition and microstructure of random copolymers prepared by SFRP are not significantly different from those of copolymers synthesized conventionally. These two observations support the conclusion that the presence of nitroxide in the SFR process does not influence the monomer reactivity ratios or the stereoselectivity of the propagating radical chain. Rather, the SFR propagation mechanism is essentially the same as that of the conventional free radical copolymerization process. 

Since its discovery in 1993 [27], nitroxide-mediated polymerization (NMP) has been the most extensively studied technique from the dissociation-combination dass of LRP mechanisms (Scheme 13.7). This method is also commonly termed stable free radical polymerization (SFRP). NMP reactions are distinguished by the use of stable free radical nitroxide molecules (N ) as the controlling agent [e.g. 2,2,6,6-tetramethylpiperidin-l-oxyl (TEMPO), (l-diethylphosphono-2,2-dimethyl)propyl nitroxide (DEPN)]. 

The unexpected good control in the incorporation of borane groups to polyolefin by metallocene catalysis and the subsequent radical chain extension by the incorporated borane groups prompted us to examine this free radical polymerization mechanism in greater details. Several relatively stable borane-based radical initiators were discovered, which exhibited living radical polymerization characteristics, with a linear relationship between polymer molecular weight and monomer conversion [27] and producing block copolymers by sequential monomer addition [28]. This stable radical... 

In most reports, the peptide-polymer-conjugates are prepared by using a polymeric macroinitiator for the polymerization of the polypeptide however, the sequence can also be reversed. Polypeptides can be prepared and used as macroinitiators for a polymerization. Particularly suited for this approach are controlled polymerization techniques because they usually allow good end-group control and adjustment of the molecular weight and the molecular weight distribution of the polymer block. There are different mechanisms for a controlled radical polymerization that can be used for this purpose stable free-radical polymerization (SFRP), ATRP, and reversible addition fragmentation chain transfer (RAFT) polymerization. 

Most of the LFRP research ia the 1990s is focused on the use of nitroxides as the stable free radical. The main problems associated with nitroxide-mediated styrene polymerizations are slow polymerization rate and the iaability to make high molecular weight narrow-polydispersity PS. This iaability is likely to be the result of side reactions of the living end lea ding to termination rather than propagation (183). The polymerization rate can be accelerated by the addition of acids to the process (184). The mechanism of the accelerative effect of the acid is not certain. 

Radical hydrosilylation takes place according to a usual free-radical mechanism with silyl radicals as chain carriers. Products are formed predominantly through the most stable radical intermediate. Even highly hindered alkenes undergo radical hydrosilylation. This process, however, is not stereoselective, and alkenes that are prone to free-radical polymerization may form polymers. 

Atom transfer free-radical polymerization (ATRP) proceeds by a transient/ stable radical mechanism analagous to nitroxide-mediated free-radical polymerizations (see Section 3). This controlled polymerization concept was first described independently by two research groups in 1995, and exhibits a high degree of control over the molecular weight of the desired polymer and more remarkably, the ability to realize very narrow molecular weight distributions < 1.05). ATRP methodologies involve (see... 

In this mechanism of polymerization, a small amount of free radicals is generated. These attack the carbon-carbon double bonds of monomer molecules, bond to one carbon, and produce the more stable free radical this is the initiation step. Since few chains are initiated, the free radical attacks yet another monomer, adds to the double bond, and forms another free radical that, in turn, continues the process this is propagation. Eventually two developing free radical chains may bond together and terminate the chain reaction. 

Polytetrafluoroethylene is a completely fluorinated polymer manufactured by free-radical polymerization of tetrafluoroethylene. With a linear molecular structure of repeating -CF2—CF2- units, PTFE is a crystalline polymer with a melting point of 326.7°C. Its specific gravity is 2.13—2.19. Polytetrafluoroethylene has exceptional resistance to chemicals. Its dielectric constant (2.1) and loss factor are low and stable across a wide range of temperature. It has useful mechanical properties from myogenic temperatures to 260°C. In the United States, PTFE is sold as Halon, Algoflon, Teflon, Fluon, Hostaflon, and Polyflon. ... 

The fifty chapters submitted for publication in the ACS Symposium series could not fit into one volume and therefore we decided to split them into two volumes. In order to balance the size of each volume we did not divide the chapters into volumes related to mechanisms and materials but rather to those related to atom transfer radical polymerization (ATRP) and to other controlled/living radical polymerization methods reversible-addition fragmentation transfer (RAFT) and other degenerative transfer techniques, as well as stable free radical pol5mierizations (SFRP) including nitroxide mediated polymerization (NMP) and organometallic mediated radical polymerization (OMRP). 

Poly(vinyl acetate) (PVA) and ethylene-vinyl acetate (EVA) copolymer adhesives have much in common, yet represent extremes in the degree of sophistication of their production processes. Both products are stable suspensions in water of a film-forming polymer, the particles of which are generally spherical. They are made by emulsion polymerization, which uses a free-radical addition mechanism to polymerize the monomer in the presence of water and stabilizers. Vinyl acetate is the sole or major monomeric raw material. 

Free-radical polymerizations of certain monomers exhibit autoacceleration at high conversion via an additional mechanism, the isothermal gel effect or Trommsdorff effect (23-26). These reactions occur by the creation of a radical that attacks an unsaturated monomer, converting it to a radical, which can add to another monomer, propagating the chain. The chain growth terminates when two radical chains ends encounter each other, forming a stable... 

One of the limitations of anionic polymerization with respect to preparation of block copolymers is the rather limited range of monomers that can be polymerized anionically to form polymers with well-defined stmctures. One solution to this problem is to utilize anionic polymerization to form a well-defined polymer that is functionalized with an end group that can be used to initiate polymerization via another polymerization method, for example, controlled free-radical polymerization. One such functional group is the aminoxy group which can be used to initiate nitroxide-mediated radical polymerization (NMP). °° PSLi has been reacted with 4-methoxy-2,2,6,6-tetramethylpiperidin-1-oxyl (MTEMPO), a stable nitroxide free radical, in THF at -78 °C as shown in eqn [30]. The mechanism of this functionalization was presumed to occur... 

One of the nice features of free-radical polymerization is that values of the preexponential coefficients and activation energies (or alternately half-life values at various temperatures) can be obtained in the literature (such as in Odian (1991)) or from their manufacturers (such as Wako Chemical Corp.) for a variety of initiators, and these numbers do not normally change no matter what the fluid environment the initiator molecules are in. Thus, if we want to decompose more than 99% of the starting initiator material in the reactor, we just have to wait for the reaction to proceed up to five times the initiator half-life. The other attractive feature of free-radical polymerization is that free-radical reactions are well known and radical concentrations can be directly measured. Thus, we know, for example, that if we want to preserve radicals in solution, we should not allow oxygen gas (O2) in our system, because reactive radicals will combine with oxygen gas to form a stable peroxy radical. That is why reaction fluids were bubbled with N2, CO2, Ar, or any inert gas, in order to displace O2 gas that comes from the air. Finally, Iree-radical polymerization is not sensitive to atmospheric or process water, compared to other polymerization kinetic mechanisms. 

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