Octadiene polymer

B. Maxwell (Princeton University, Princeton, New Jersey) I just want to respond to the comment that I can easily make the octadiene polymer. Only once in my life have I made a polymer, and it was a phenolic resin. It wouldn t be easy for me. If anyone wants to make a polymer for me. I ll be glad to test it to see what happens. 

Some of the most difficult heterophase systems to characterize are those based on hydrocarbon polymers such as mbber-toughened polypropylene or other blends of mbbers and polyolefins. Eecause of its selectivity, RuO staining has been found to be usehil in these cases (221,222,230). Also, OsO staining of the amorphous blend components has been reported after sorption of double-bond-containing molecules such as 1,7-octadiene (231) or styrene (232). In these cases, the solvent is preferentially sorbed into the amorphous phase, and the reaction with OsO renders contrast between the phases. 

The organoboron polymer complex was prepared as follows. First, poly(organoboron halide)55 was prepared according to the reported method, by hydroboration polymerization between 1,7-octadiene and the monobromoborane dimethylsuffide complex. The polymer obtained was then reacted with half an equivalent of methanol and 1-methylimidazole to give the corresponding copolymer efficiently (scheme 4). The structure of the polymer was characterized by H- and UB-NMR spectra. 

Hydroarylation of alkenes is applied to achieve step-growth co-polymerization of aromatic ketones and ct,c< -dienes such as 3,3,6,6-tetramethyl-3,6-disila-l,7-octadiene and 1,3-divinyltetramethyldisiloxane. Co-polymerization of acetophenone and 3,3,6,6-tetramethyl-3,6-disila-l,7-octadiene is catalyzed by Ru species which has been previously activated by treatment with styrene, and a significantly high molecular weight co-polymer, co-poly(3,3,6,6-tetra-methyl-3,6-disila-l,8-octanylene/2-acetyl-l,3-phenylene), is obtained (Scheme 21 ).166... 

Cyclopolymerization of Nonconjugated Dienes. Cyclopolymerization is an addition polymerization that leads to introduction of cyclic structures into the main chain of the polymer. Nonconjugated dienes are the most deeply studied monomers for cyclopolymerization and for cyclocopolymerizations with alkene monomers 66 In general, (substituted and unsubstituted) dienes with double bonds that are linked by less than two or more than four atoms cannot undergo efficient cyclization and result in crosslinked materials.12 In fact, efficient cyclopolymerization processes have been described, for instance, for a,oo-dienes like 1,5-hexadiene, 2-methyl-l,5-hexadiene, 1,6-heptadiene, and 1,7-octadiene,67 73 which lead to formation of homopolymers and copolymers containing methylene-1,3-cycloalkane units. 

Hence, two methods are available that can be applied to follow nanoparticles formation and growth (i) an indirect method that utilizes the consumption of molecular hydrogen pressure versus time and (ii) a direct method that follows the loss of precursor by the 1 1 conversion of its cyclo-octadiene ligand to cyclo-octane by GLC measurements. The mechanism developed by Watzky and Finke suggests that the nanoparticles act as Hving-metal polymers -a concept that could be used to obtain particles with defined sizes simply by adding the appropriate amounts of catalyst precursors [32]. 

A study on the homo- and copolymerization of a variety of dienes such as 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, E-l,3-pentadiene, E-l,3-hexadiene, E-l,3-heptadiene, E-l,3-octadiene, E,E-2,4-hexadiene, E-2-methyl-l,3-pentadiene, 1,3-cyclohexadiene mainly focused on mechanistic aspects [139]. It was shown that 1,4-disubstituted butadienes yield frans-1,4-polymers, whereas 2,3-disubstituted butadienes mainly resulted in cis- 1,4-polymers. Polymers obtained by the polymerization of 1,3-disubstituted butadienes showed a mixed trans-1,4/cis-1,4 structure (60/40). The microstructures of the investigated polymers are summarized in Table 26. 

The hydrogenation of 1,5-cyclo-octadien (COD) to cyclo-octene (COE) is performed in a slurry reactor. The reaction is relevant because the product is an intermediate for the production of special polymers. However, this reaction suffers from the drawback that the hydrogenation does not stop at cyclo-octene, because a full hydrogenation to cyclo-octane (COA) is possible, as shown in Figure 4.1.12. 

Dimerization of butadiene is used for the selective formation of 1,5-cyclo-octadiene (1,5-COD), which on selective hydrogenation gives cyclooctene. By ring-opened metathesis polymerization of cyclooctene a specialty polymer is obtained (see Section 7.6.1). Hulls sells this polymer as Vestenamer . 

With AgC104, 1,5-hexadiene, 1,7-octadiene, and 1,9-decadiene form 3 2, 1 1, and 1 1 complexes, respectively (85a). The 1 1 complexes are considered (85a) to be coordination polymers while the 3 2 complex of 1,5-hexadiene has been shown (45a) to have chelated diene-silver ion entities connected through a bridging diene molecule to produce a distorted trigonal coordination about the metal. 

Other approaches include the use of difunctional olefins such as 1,7-octadiene, 1,9-decadiene, or para-(3-butenyl)styrene.875 While the former method also generates chain cross-linking (thus unprocessable polymer gels), the latter leads only to LCB formation through hydrogenolysis after a secondary styrene insertion. Tandem Zr/Fe catalysis has been used as well.876 The preparation of iPP with PS branches has been achieved by co-polymerization of propylene with allyl-terminated PS macromonomers.877... 

Non-conjugatively linked 9,9/-dibenzosilole polymers have also been reported [44,45]. In an early paper, a dehydrogenation catalyst, bis(l,5-cyclo-octadiene)palladium, was used in the synthesis of poly(9,9-dibenzosilole) 52 (Scheme 6) [45]. Recently, poly(dibenzosilole-vinylene)s 54 were obtained from the platinum-catalysed hydrosilylation of 9,9-dihydrodibenzosilole 51 with 9,9-diethynyldibenzosilole 53 (Scheme 6) [44]. 

Et(Ind)2ZrCl2/MAO gives copolymers of ethylene or propylene with nonconjugated dienes, such as 2-methyl-1,4-pentadiene, 7-methyl-1,6-octadiene and 1,7-octadiene, (Eq. 23) [103]. rac-Et(Ind)2ZrCl2/MAO also catalyzes copolymerizations of asymmetrically substituted linear dienes, 6-phenyl-1,5-hexadiene, 7-methyl-1,6-octadiene, and R-(+)-5,7-dimethyl- 1,6-octadiene. The copolymerization of R-(+)-5,7-dimethyl-l,6-octadiene with propylene to give the polymer with ca. 15% diene incorporation. The ratio of the diene-derived part is ca. 15% of the polymer [104]. 

With still longer intervening organic moieties, strain-free cyclosiloxanes result, e.g., the seven-membered 2,2,7,7-tetramethyl-l-oxa-2,7-disilacycloheptane and its polymers . The ultimate extension of this cyclocarbosiloxane synthesis is illustrated by the next example. Hydrosilylation of both ends of 1,7-octadiene with HMejSiCl gives an adduct that upon hydrolysis yields -f-Me2Si(CH2)8SiMe20-, which in turn affords the 22-membered dimeric and 11-membered monomeric cyclosiloxanes upon alkaline thermolysis . 

Starting material for the preparation of the major component of its pheromone bouquet is 1 -phenoxy-(2 ,7)-octadiene, which is accessible by telomerisa-tion of butadiene on a noble metal catalyst Butadiene telomers find nowadays extensive use as plasiticiser alcohols, solvents, corrosion inhibitors and monomers for polymers. 

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