Narrower polydispersity

More recent process research aimed at anionic PS is that of BASF AG. Unlike the Dow Process, the BASF process utilizes continuous linear-flow reactors (LFR) with no back-mixing to make narrow polydispersity resins. This process consists of a series alternating reactors and heat exchangers (Fig. 22). Inside the reactors, the polymerization exotherm carries the temperature from 30°C at the inlet to 90°C at the outlet. The heat exchangers then take the temperature back down to 30°C. This process, which requires no solvent, results in the formation of narrow polydispersity PS. 

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. 

Poly(MA-CDA) was synthesized as described previously by a free radical copolymerization followed by hydrolysis in aqueous solution. By the fractional precipita- n of the copolymerization product (MW = 14,200, MW/Mn = 3.1) different average-molecular weight po-ly(M A-CDA)s with narrow polydispersity were obtained as shown in Table 2. 

As in the case of PS (Section 8.2.1) polymers formed by living radical polymerization (NMP, ATRP, RAFT) have thermally unstable labile chain ends. Although PMMA can be prepared by NMP, it is made difficult by the incidence of cross disproportionation.42 Thermal elimination, possibly by a homolysis-cross disproportionation mechanism, provides a route to narrow polydispersity macromonomers.43 Chemistries for end group replacement have been devised in the case of polymers formed by NMP (Section 9.3.6), ATRP (Section 9.4) and RAFT (Section 9.5.3). 

The new knowledge and understanding of radical processes has resulted in new polymer structures and in new routes to established materials many with commercial significance. For example, radical polymerization is now used in the production of block copolymers, narrow polydispersity homopolymers, and other materials of controlled architecture that were previously available only by more demanding routes. These commercial developments have added to the resurgence of studies on radical polymerization. 

The development of controlled/living radical polymerization processes, yielding polymers with narrow polydispersities and a high percentage of liv-... 

We have demonstrated a new class of effective, recoverable thermormorphic CCT catalysts capable of producing colorless methacrylate oligomers with narrow polydispersity and low molecular weight. For controlled radical polymerization of simple alkyl methacrylates, the use of multiple polyethylene tails of moderate molecular weight (700 Da) gave the best balance of color control and catalyst activity. Porphyrin-derived thermomorphic catalysts met the criteria of easy separation from product resin and low catalyst loss per batch, but were too expensive for commercial implementation. However, the polyethylene-supported cobalt phthalocyanine complex is more economically viable due to its greater ease of synthesis. 

A series of bis(phenoxide) aluminum alkoxides have also been reported as lactone ROP initiators. Complexes (264)-(266) all initiate the well-controlled ROP of CL, NVL.806,807 and L-LA.808 Block copolymers have been prepared by sequential monomer addition, and resumption experiments (addition of a second aliquot of monomer to a living chain) support a living mechanism. The polymerizations are characterized by narrow polydispersities (1.20) and molecular weights close to calculated values. However, other researchers using closely related (267) have reported Mw/Mn values of 1.50 and proposed that an equilibrium between dimeric and monomeric initiator molecules was responsible for an efficiency of 0.36.809 In addition, the polymerization of LA using (268) only achieved a conversion of 15% after 5 days at 80 °C (Mn = 21,070, Mn calc 2,010, Mw/Mn = 1.46).810... 

A more active zinc catalyst has been developed containing a /3-diketiminate ancillary ligand.823 Complex (272) converts 200 equivalents rac-LA. in less than 20 min at room temperature to highly heterotactic PLA (the probability of a racemic junction between monomer units, PR = 0.90 at 25 °C and 0.94 at 0°C) of narrow polydispersity (Mn = 37,900, Mn calc = 28,800, Mw/Mn= 1.10). Kinetic studies reveal that the zinc initiators display a fractional rate law order (1.56 0.06). In accord with the observation that kR/ss > kR/RR (or ks/RR > ks/ss), the polymerization of L-LA proceeds significantly slower than rac-LA (kapp L-LA = 0.031 min-1 kapp rac-LA = 0.22 min-1).824... 

If mono-hydroxyl functionalized polyethylene glycol), HO-PEG, is added to Ca(NTMS2)2.THF2, then addition of LA affords the diblock PEG-b-PLA (Mn= 15,500, Mn calc = 15,500, Mw/Mn = 1.03).832 Using a similar strategy the reaction of CaFI2 with telechelic diol HO-(PEG)-OH, followed by polymerization of L-LA results in a triblock structure, PLA-b-PEG-b-PLA of narrow polydispersity (1.02-1.08).835 836 Triblock copolymers of morpholine-2,5-diones with PEO have also been prepared in this manner.837... 

Bis(ethylacetoacetonate)-lanthanide(III) alkoxides, represented by structure (314), also initiate the well-controlled ROP of CL.895 Mn increases linearly with conversion (with Mw/Mn<1.10 throughout), and increasing [M]0/[I]o- Kinetic analysis implies a first order dependence on the lanthanide initiator, consistent with a non-aggregated active site. Block copolymers with moderately narrow polydispersities (1.25-1.45) have also been prepared using these initiators. NMR spectroscopy confirms well-controlled block sequences suggesting that these initiators are less susceptible to transesteriflcation than other lanthanide alkoxides. Initiation occurs exclusively at the alkoxide bond, and the tris(ethylacetoacetonate) analogs are inactive under the same conditions. 

Dextrans are also attractive as macromolecular carriers of paramagnetic chelates because of their hydrophilicity, the different available molecular weights with narrow polydispersity, and the versatility of activation methods applicable. Several DTPA- or DOTA-loaded carboxymethyl dextran (CMD) derivatives have been prepared and tested in blood pool MRI.136-139 The relaxivities reported for these compounds are, however, relatively moderate. 

Living radical polymerizations have received considerable attention because they provide a convenient alternative for synthesizing block copolymers, polymers of narrow polydispersity and complex polymer structures (1-5). Because of their ability to initiate living free radical polymerizations, iniferters have been examined extensively after Otsu et al. (6) introduced them in 1982. In particular, dithiocarbamate derivatives have been studied more closely by several researchers. Lambrinos et al (7) have examined the molecular weight evolution during the polymerization of n-butyl acrylate using p-x ylylene bis(A,A-diethyl... 

Microspheres were monitored by scanning electron microscopy (SEM JEOL 35C), and their diameters were determined from the corresponding SEM microphotographs. Typically, ca. 500 particles in randomly sampled areas of microsphere specimens were analyzed. Molecular weight of poly(L-Lc) was determined by GPC. A system consisting of a LKB 2150 pump, Ultrastyragel 1,000, 500, 100, 100 columns, and Wyatt Optilab 903 interferometric refractometer was used for the measurements. GPC traces were analyzed by using calibration with narrow polydispersity < 1.15)... 

An interesting feature of this enzymatic polymerization in [BMIM]PF6 is that the polymeric material exhibited remarkably narrow polydispersity values, Mw/Mn = 1.04-1.03, a value that was maintained in the seven-day test. The authors related this value to the insolubility of the polymer formed in the ionic liquid after it exceeds a certain molecular weight limit. This observation opens the possibility of tailoring ionic liquids with varying solvating abilities for structural manipulation of desired polymeric material. 

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