Co-polymerization

Popcorn Polymerization CO-Polymerization, frequendy referred to as popcorn polymerization because of the appearance of the product, can be a dangerous side reaction if not carefully controlled. The polymeriza tion appears to proceed without external initia tion (69—71), and is catalyzed by the tightly gelled polymer seeds that are a product of the polymerization. Once seeds are present and immersed either in the Hquid or vapor phase of monomer, their weight increases exponentially with time. 

Suspension (co)polymerization is carried out in aqueous solutions of monomers dispersed in the form of 0.1-5 mm diameter droplets by stirring in nonmixed water-organic liquids in the presence of initiators. The organic liquids that are not dissolving monomers and (co)polymers are represented by solvents that either form azeotropic water mixtures (toluene, heptane, cy-... 

Homopolymerization of macroazoinimers and co-polymerization of macroinimers with a vinyl monomer yield crosslinked polyethyleneglycol or polyethyleneglycol-vinyl polymer-crosslinked block copolymer, respectively. The homopolymers and block copolymers having PEG units with molecular weights of 1000 and 1500 still showed crystallinity of the PEG units in the network structure [48] and the second heating thermograms of polymers having PEG-1000 and PEG-1500 units showed that the recrystallization rates were very fast (Fig. 3). 

Amine-terminated siloxane oligomers have also been utilized in the synthesis of various siloxane-amide and siloxane-imide copolymers, High molecular weight siloxane-amide copolymers have been synthesized by the solution or interfacial co-polymerization of siloxane oligomers with sebacoyl chloride or terephthaloyl chloride respectively 1S5,165). In some reactions diamine chain extenders have also been utilized. Thermal and dynamic mechanical characterization of these copolymers have shown the formation of multiphase systems160). Compression molded films displayed very good elastomeric properties. 

The distinction between the rates of homo- and copolymerization apparently is misapprehended by some workers. For example, a recent review 141) discusses the results of McGrath 142) who reported butadiene to be more reactive in polymerization in hexane than isoprene, whether with respect to lithium polybutadiene or polyisoprene, although the homopropagation of lithium polyisoprene in hexane was found to be faster than of polybutadiene. The miscomprehension led to the erroneous statement14l) McGrath 142) results regarding the rate constants for butadiene and isoprene place in clear perspective the bizarre assertion 140) that butadiene will be twice as reactive as isoprene (in anionic co-polymerization). 

Michalak A, Ziegler T (2005) Late Transition Metal as Homo- and Co-Polymerization Catalysts. 12 145-186... 

Advanced computational models are also developed to understand the formation of polymer microstructure and polymer morphology. Nonuniform compositional distribution in olefin copolymers can affect the chain solubility of highly crystalline polymers. When such compositional nonuniformity is present, hydrodynamic volume distribution measured by size exclusion chromatography does not match the exact copolymer molecular weight distribution. Therefore, it is necessary to calculate the hydrodynamic volume distribution from a copolymer kinetic model and to relate it to the copolymer molecular weight distribution. The finite molecular weight moment techniques that were developed for free radical homo- and co-polymerization processes can be used for such calculations [1,14,15]. 

Figure 2. Representative optical micrographs of poly-HEMA cross-linked with EDMA. (a) and (b) represent the gel-type polymer produced by suspension co-polymerization in the dry and swollen state, respectively, (c) and (d) represent the macroreticular polymer produced by suspension co-polymerization in the presence of a porogen (toluene), in the dry and swollen (vide infra) state, respeetively [13], (Reprinted from Ref [15], 1996, with permission from Elsevier.)...

The use of y-ray induced radical pol5unerization proved to be a successful alternative for the radical co-polymer-ization of metal complexes with ligands containing acrylic C—C double bonds [100-102,129,130]. In particular, the palladium(II) complex cw-[PdCl2(ICPA)2] (1, Scheme 4) was co-polymerized in DMF solution with DMA and MBAA (cross-linker, 4% mol), with no degradation of the metal center [100,101]. 

The reduction of palladium(II) with an alcoholic solution of NaBH4 [101] or by treatment in situ of the methanol-swollen material under hydrogen [129] yielded a supported palladium catalyst, referred to as self supported by the authors [101,129]. The same co-polymerization reaction was carried out inside the nanopores of a DMF-swollen gel-type resin made by DMA and MBAA (crosslinker, 4% mol) [101,129], thus obtaining a sequential IPN [131]. Also this material was transformed into a... 

GPC proved to be a method extraordinarily well suited to the analysis and purification of 9-phenylcarbazole monodendrons, naturally branched polymers.12 Monodendrons up to generation four, molecular weight 16.6 kDa, were separated by GPC. Branching, introduced into bacterially produced poly(hydroxy butyrate) by co-polymerization with hydroxyvaleric acid, was analyzed by GPC in chloroform with on-line viscometry.13... 

Monolithic columns, formed from the co-polymerization of divinylbenzene and vinylbenzyl chloride or styrene, were observed to be resistant to bubble formation.11 Application of pressure in electrochromatography, discussed below, also reduces bubble formation. A massively parallel detector capable of scanning up to 1000 capillaries using planar confocal fluorescence has been used for DNA sequencing.1213 Recovery of fluorescence following pho-tobleaching has been used to measure DNA mobility in agarose gel.14... 

A variety of reagents could be used to carry out such a conversion (18,19). We chose to react the alkoxide ion with succinic anhydride (SA), because the alkoxide ion could be converted quantitatively to the carboxylate ion when excess of SA is used, and also because no side reactions are reported (19). The carboxylate anion, 3, thus formed was used to polymerize PVL giving the masked poly(oxyethylene)-b-po y(pivalolactone) co-polymeric salt, 4. The salt, 4, was converted to the teiechelomer, 5, by acid hydrolysis.. ... 

All grafted samples are extracted in water for 24h before they are analyzed and most homopolymer is then washed off. It is concluded from these experiments that graft-co-polymerization occurs predominantly during the early stages of the reaction. In the later stages (here after about 20 min.) we have mainly homopolymerization. 

Production of poly(3HB-co-3HV) co-polymer in plants has recently been demonstrated by the PHA group of Monsanto [27], which acquired the PHA business of Zeneca in 1996. In the commercial production of poly(3HB-co-3HV) from R. eutropha, propionate is added to the growth media in order to create an intracellular pool of propionyl-CoA which can be condensed to acetyl-CoA to form 3-ketovaleryl-CoA. The 3-ketovaleryl-CoA is then reduced by the aceto-acetyl-CoA reductase to give 3-hydroxyvaleryl-CoA, which is co-polymerized with 3-hydroxybutyryl-CoA to synthesize poly(3HB-co-3HV) (Fig. 1). For the synthesis of poly(3HB-co-3HV) in plants, it was thus necessary to create an endogenous pool of propionyl-CoA which could be used by the PHA pathway. 

Beyond these fundamental aspects, the great versatility of organozinc compounds can also be seen in the important roles they play in commercial applications. Organozinc complexes have been shown to be excellent catalysts and precatalysts for the polymerization of esters and the co-polymerization of epoxides and carbon dioxide they are also co-catalysts in polyolefin catalysis. 

Zinc compounds have recently been used as pre-catalysts for the polymerization of lactides and the co-polymerization of epoxides and carbon dioxide (see Sections 2.06.8-2.06.12). The active catalysts in these reactions are not organozinc compounds, but their protonolyzed products. A few well-defined organozinc compounds, however, have been used as co-catalysts and chain-transfer reagents in the transition metal-catalyzed polymerization of olefins. 

The addition of a large excess of bis(cj-alkenyl)zinc compounds to the TiC -catalyzed polymerization of propene resulted in an increased polymer yield, but a reduction in the molecular weights of the polymers.64 This suggests that the diorganozinc compounds are both co-catalysts and chain-transfer agents in this polymerization. The catalyst activity decreased in the order bis(3-butenyl)zinc < bis(7-octenyl)zinc < chlorodiethylaluminum. Bis(7-octenyl)zinc was co-polymerized with propene to afford hexylzinc side chains, whose zinc-carbon moieties were converted to vinyl groups by the addition of allyl bromide. 

Organozinc diiminates of various ligand platforms (particularly /2-diketiminates (BDIs)) have been used extensively in catalysis, especially for the polymerizations of lactides and epoxides and the co-polymerization of epoxides with carbon dioxide. 

The interactions of dimethyl- and diethylzinc with bulky tris(hydroxyphenyl)methanes, Scheme 86, yielded, depending on the reaction conditions, a variety of alkylzinc alkoxides, featuring two-, three-, and four-coordinate zinc centers. These polynuclear compounds (Figure 63 shows the trinuclear ethylzinc derivative 136) are relatively poor catalysts for the co-polymerization of cyclohexene oxide and carbon dioxide.197... 

A chiral ethylzinc aminoalkoxide 147, synthesized by the addition of ZnEt2 to (cyclohexene oxide with C02 in almost quantitative yield and with an ee of 49%. This value is somewhat lower than that obtained by the same authors from the in situ generated monomeric form of the catalyst, which furnished product with an ee of 70%.213... 

---