Polymerization first reported

Group transfer polymerization, first reported by DuPont in 1983 (103), allows the production of methacrylic esters with controlled architectures. This technique uses a silyl ketene acetal initiator to produce block polymers, comb-graft pol3uners, star polymers, and functional polymers (103,104). 

Polymerization of compounds perfonned with UV light was first reported in the 1970s [86] and was followed by further studies [87, 88 and 89]. Another study was concerned with the deposition and polymerization of multilayers of alcohols and acids incoiyDorating the diene group, -CH=CH-CH=CH-, at the hydrophilic end of the molecule [90]. 

Microtubulin Polymerization Inhibitors. The ben2imida2oles were first reported to have systemic fungicidal activity in 1964 (29). Prominent examples include thiabendazole [148-79-8] (42) fuberida2ole [3878-19-1] (43) carbendazim [10605-21-7] (44) benomyl [17804-35-2] (45) and thiophanate methyl [23564-05-8] (46). Benomyl (45), the most widely used member of this group is almost certainly inactive as a fungicide until it is converted in plants and soil to carbendazim (44). Likewise, thiophanate and thiophanate methyl (46) are nonfungitoxic until converted to carbendazin (44). 

The anionic polymerization of methacrylates using a silyl ketene acetal initiator has been termed group-transfer polymerization (GTP). First reported by Du Pont researchers in 1983 (100), group-transfer polymerization allows the control of methacrylate molecular stmcture typical of living polymers, but can be conveniendy mn at room temperature and above. The use of GTP to prepare block polymers, comb-graft polymers, loop polymers, star polymers, and functional polymers has been reported (100,101). 

Heterogeneous Catalytic Polymerization. The preparation of polymers of ethylene oxide with molecular weights greater than 100,000 was first reported in 1933. The polymer was produced by placing ethylene oxide in contact with an alkaline-earth oxide for extended periods (61). In the 1950s, the low yield and low polymerization rates of the eady work were improved upon by the use of alkaline-earth carbonates as the catalysts (62). 

Prepa.ra.tion, The preparation of amorphous high (99%) 1,2-polybutadiene was first reported iu 1981 (27). The use of a heterocycHc chelating diamine such as dipiperidine ethane iu the polymerization gave an amorphous elastomeric polymer of 99.9% 1,2 units and a glass-transition temperature of +5°C. In a previous description (53,54) of the use of a chelating diamine such as A/A/N(N -tetramethylethylene diamine, an 80% 1,2-polybutadiene with a glass-transition temperature of —30°C was produced. 

The preparation of a synthetic polyisoprene was first reported in 1879 by Bouchardat (1), who treated isoprene [78-79-5] obtained from the destmctive distillation of natural mbber with hydrochloric acid. This discovery led to a search for a way of converting isoprene into a material dupHcating natural mbber (Hepea brasilienses). During World War II, scientists extensively studied the polymerization of isoprene with the hope of replicating natural mbber since the United States was temporarily cut off from sufficient natural mbber suppHes. These studies were not successful. PinaHy, in 1954 the B.E. 

Polyacetylenes. The first report of the synthesis of a strong, flexible, free-standing film of the simplest conjugated polymer, polyacetylene [26571-64-2] (CH), was made in 1974 (16). The process, known as the Shirakawa technique, involves polymerization of acetylene on a thin-film coating of a heterogeneous Ziegler-Natta initiator system in a glass reactor, as shown in equation 1. 

Strohmeier and Hartmann [14] first reported in 1964 the photoinitiation of polymerization of ethyl acrylate by several transition metal carbonyls in the presence of CCI4. Vinyl chloride has also been polymerized in a similar manner [15,16] No detailed photoinitiation mechanisms were discussed, but it seems most likely that photoinitiation proceeds by the route shown in reaction Scheme (9). 

The incorporation of thermally labile azo groups into polymer backbones was first reported in the early 1950s [2]. Since then, numerous techniques for synthesizing azo-containing polymers have been developed. The effort to create new azo-containing polymeric materials has been reviewed by several authors [3-8]. 

The first steps towards living radical polymerization were laken by Otsu and colleagues283 in 1982. In 1985, this was taken one step further with the development by Solomon et al.l0 of nitroxide-mediated polymerization (NMP). This work was first reported in the patent literature30 and in conference papers but was not widely recognized until 1993 when Georges et aL, applied the method in... 

The thermal polymerization of S has a long history.310 The process was first reported in 1839, though the involvement of radicals was only proved in the 1930s. Carefully purified S undergoes spontaneous polymerization at a rate of ca 0.1% per hour at 60 C and 2% per hour at 100 °C. At 180 aC, 80% conversion of monomer to polymer occurs in approximately 40 minutes. Polymer production is accompanied by the formation of S dimers and trimers which comprise ca 2% by weight of total products. The dimer fraction consists largely of cis- and trans-1,2-diphenylcyclobutanes (90 and 91) while the stereoisomeric tetrahydronaphthalenes (92 a nd 93) are the main constituents of the trinier fraction.313... 

Thiol-ene polymerization was first reported in 1938.220 In this process, a polymer chain is built up by a sequence of thiyl radical addition and chain transfer steps (Scheme 7.17). The thiol-ene process is unique amongst radical polymerizations in that, while it is a radical chain process, the rate of molecular weight increase is more typical of a step-growth polymerization. Polymers ideally consist of alternating residues derived from the diene and the dithiol. However, when dienes with high kp and relatively low A-, monomers (e.g. acrylates) are used, short sequences of units derived from the diene are sometimes formed. 

The first use of sterically hindered hexasubstituted ethanes [e.g. 33] as initiators of polymerization was reported by Bledzki et al.77,78 The use of related initiators based on silylatcd pinacols [e.g. 34, 35] has been reported by Crivcllo et a/.,7l>82 jjan( os et ai i anOther initiators of this class include 36 fi X/ and 37.The rates of decomposition of hexasubstituted ethanes and the derived macroinitiators are known to vary according to the degree of steric... 

The first reports of ATRP (Atom Transfer Radical Polymerization), which clearly displayed the characteristics of living polymerization, appeared in 1995 from the Laboratories of Sawamoto,2 Matyjaszewski266 and Percec.267 The literature on ATRP is now so vast that a comprehensive review cannot be... 

In contrast to the situation with copper-based catalysis, most studies on ruthenium-based catalysts have made use of preformed metal complexes. The first reports of ruthenium-mediated polymerization by Sawamoto and coworkers appeared in I995.26 In the early work, the square pyramidal ruthenium (II) halide 146 was used in combination with a cocatalyst (usually aluminum isopropoxide). 

In 1968 DairOlio et al. published the first report of analogous electrosyntheses in other systems. They had observed the formation of brittle, filmlike pyrrole black on a Pt-electrode during the anodic oxidation of pyrrole in dilute sulphuric acid. Conductivity measurements carried out on the isolated solid state materials gave a value of 8 Scm . In addition, a strong ESR signal was evidence of a high number of unpaired spins. Earlier, in 1961, H. Lund had reported — in a virtually unobtainable publication — that PPy can be produced by electrochemical polymerization. 

Another innovative approach to controlling amine-initiated NCA polymerizations was reported in 2003 by Schlaad and coworkers [20]. Their strategy was to avoid formation of NCA anions, which cause significant chain termination after rearranging to isocyanocarboxylates [11, 12], through use of primary amine hydrochloride salts as initiators. The reactivity of amine hydrochlorides with NCAs was first explored by the group of Knobler, who found that they could react... 

Kunitake and coworkers3 first reported the cationic polymerization of vinylferrocene, and Korshak and co-workers33 polymerized 1,1 -diisopropenylferrocene with cationic initiators. Recently,... 

The first synthesis of Kevlar by solution polymerization was reported by S. L. Kwolek, P. W. Morgan, and W. R. Gorenson of DuPont in U. S. Patent 3,063,966 (1962). In 1980, Stephanie Kwolek won the American Chemical Society s Award for Creative Invention, and on July 22, 1995, she was inducted into the National Inventors Hall of Fame in Akron, Ohio. In 1996 Stephanie Kwolek was awarded... 

Poly(difluorophosphazene). A brief mention will be made of poly(difluorophosphazene) (NPF2)n, which was first reported by Seel and Langer (23) and has been investigated in greater detail by Allcock (24). It is prepared by the bulk polymerization of hexafluorocyclotriphosphazene (NPF2)g at 350°C. 

As described in Section 9.1.2.2.3, several lanthanocene alkyls are known to be ethylene polymerization catalysts.221,226-229 Both (188) and (190) have been reported to catalyze the block copolymerization of ethylene with MMA (as well as with other polar monomers including MA, EA and lactones).229 The reaction is only successful if the olefin is polymerized first reversing the order of monomer addition, i.e., polymerizing MMA first, then adding ethylene only affords PMMA homopolymer. In order to keep the PE block soluble the Mn of the prepolymer is restricted to <12,000. Several other lanthanide complexes have also been reported to catalyze the preparation of PE-b-PMMA,474 76 as well as the copolymer of MMA with higher olefins such as 1-hexene.477... 

The anionic polymerization of isocyanates using NaCN as an initiator was first reported in I960.998 The living coordinative polymerization of n-hexylisocyanate has been described using the titanium(IV) complexes (345) (348).999-1001 A trifunctional initiator has also been used to prepare star polyisocyanates.1002... 

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