Polymers dimerization

Interestingly, the Fe2+ ion in the core can be easily removed by base, the complex dissociates and the individual polymer dimers can be analyzed. Block copolymers of 2-ethyl-2-oxazoline with other substituted oxazolines have also been made [121]. Ru2+(4,4 dichloromethyl-2,2 bipyridine)3 has also been used as the multifunctional initiator for the ATRP of styrene at 110°C [122], It is interesting to note that the Cu+ ions necessary for the polymerization reaction are solubilized via complexation with other bipyridine species. 

To date, the crystal structures of several a-lithiated ethers have been determined" . Despite the aggregation, i.e. polymers, dimers or monomers, depending on the solvation. 

The highly substituted derivative 186, in the form of the potassium salt, has been recommended for use in detonators in place of the more dangerous mercury fulminate. l,2,3-Benzotriazine-4-thione (39, R — H) has been used in photographic transfer emulsions as an inhibitor and toning agent, and heavy metal salts of the oxygen analog 10, R = H are employed as photodevelopable emulsions. The latter compound is also claimed to be useful as a stabilizer in olefin polymers and as an antioxidant in certain other polymers. Dimeric derivatives of 10 have... 

Figure 5.2 Examples of hydrogen bonding motifs used in supramolecular polymers dimerizing uieidopyrimidone (UPy) functionalized main chain supramolecular polymers (2A), simple one-point complementary hydrogen bonding interactions between pyridine and phenol (2B), and six-point complementary hydrogen bonding interaction between cyanuric acid and the Hamilton wedge receptor (2C).

Polymerization of 1,2-butylene oxide with triethyloxonium tetrafluoroborate or borontrifluoride leads to a mixture of polymer, dimer, tetramer and larger rings (7). 

Compound 70 is more stable than 68 and 69, and like 67 decomposes only at higher temperatures to give mbctures of products that have not been characterized completely. Like 62, tetrazenide 64 reacts—but faster— with PX3 (X = Cl, Br). Even at -78 C, no monomer, but only polymer [dimer (Me3SiNPX)2] is formed. 

In this review we shall focus on some of these new forms of solid carbon. The emphasis is on the physical properties of electrically conducting fullerides, fulleride polymers and nanotubes, but the neutral fullerene polymers, dimers and onion-like structures are also included for completeness. This paper is by no means a review of all important work in the domain. We fully realize that in choosing the material we had to be subjective and we selected material best known to us. A few other short reviews have been published recently on fullerene polymers on the optical properties of polymeric fullerenes [15] and on the physical properties of conducting fullerenes [16,17]. There are extensive recent reviews on the pressure and heat induced polymers [18]. We did not include in the paper the physical and chemical properties of alkali fullerides with variously charged monomer ions. These are the subject of other reviews and are described in detail in a recent monograph [19]. In particular, there are comprehensive reviews [20,21] on experiments and theories aimed at the understanding of the mechanism of superconductivity. 

Lithium butoxides increase the rate of reaction of lithium alkyls with olefins in cyclohexane or hexane but decrease it in benzene. The propagation rate is, however, decreased in both types of solvent [77, 78] according to information presently available. In fact, as far as is known, butoxides reduce rates where the mechanism has been suggested to be dissociative and increase them in the other cases. More data are still required to confirm that this always happens. The experiments with polystyryllithium [77] show that the polymer dimers in solution are not dissociated by lithium fert.-butoxide as would be expected if mixed aggregates of the type (PstLi. BuOLi ) were formed. In this case, at least, the rate effect appears to be caused by addition of butoxide to the polystyryllithium dimers. The reaction still shows half order characteristics, and the rate depression is almost complete at a 1 1 ratio of butoxide to polymer chains. The major species present in solution would seem to be (PstLi. BuOLi)2 at this point. Similar results have been obtained with polyisoprenyllithium in cyclohexane [78]. The nature of... 

The solute may exist in solution not only as a single molecule, but also in the form of certain very definite polymers (dimers,... 

We can use pC-pH diagrams that include heterogeneous equilibria for the rapid evaluation of both the total concentration of all species present as well as to provide a graphic representation of the concentrations of individual species present at various pH values. From Fig. 6-7, for example, we can deduce that in the pH range from 4.5 to 8 (which covers virtually all natural waters), FefOHla is the predominant soluble ferric iron species. The polymer (dimer) Fe2(OH)2 + does not predominate at any pH value, but it is a significant species at pH values below about 2.5. It is important to note that Fe , ferric ion, controls the solubility of Fe(OH)3tsj only below about pH 2.5. Conversely stated, at typically encountered natural water pH values in the presence of Fe(OH)3 s), Fe + is a minor component of the ferric iron species. 

Fig. 9 Synthesis of a racemic octaaryl double helix utilizing tetra[2,3-thienylene] as a core. Supramolecular self-assembly of the racemic mixture yields homochiral supramolecular polymers (dimer repeat shown).

Three different types of nucleation products have been proposed formation or sorption of polymers (dimers, trimers, etc.) on the surface (polynuclear surface complexes) a solid solution or coprecipitate that involves co-ions dissolved from the adsorbent and a precipitate formed on the surface composed of ions from the bulk solution, or their hydrolysis products (5,15,33,62,69). The two latter products are examples of surface precipitates. 

In general, it is observed that the amount of dimer and trimer contaminants is higher for poly(dienyl)lithiums versus PSLi. Thus, under conditions where the yields of carboxylated polymer, dimer, and trimer are 47, 27, and 26%, respectively, for PSLi, the corresponding yields are 27, 23, and 50% for the analogous poly (styrene-l -butadienyl) lithium. These results are once again... 

Fig. 2 Illustrative examples of mainchain LCs polymer, dimer, and monomer. The symbols given for the three dimers and two monomers are used in Fig- 3...

The viscous solutions observed at lower concentrations were turned into transparent hydrogels at concentrations >160 mg/mL. This clearly suggested that the zwitter-ionic moieties in the main backbone of the polymer dimerize to produce supramolecular crosslinks between the polymer chains which immobilize the solvent. 

Dimerization in concentrated sulfuric acid occurs mainly with those alkenes that form tertiary carbocations In some cases reaction conditions can be developed that favor the formation of higher molecular weight polymers Because these reactions proceed by way of carbocation intermediates the process is referred to as cationic polymerization We made special mention m Section 5 1 of the enormous volume of ethylene and propene production in the petrochemical industry The accompanying box summarizes the principal uses of these alkenes Most of the ethylene is converted to polyethylene, a high molecular weight polymer of ethylene Polyethylene cannot be prepared by cationic polymerization but is the simplest example of a polymer that is produced on a large scale by free radical polymerization... 

Oligomer (Section 14 15) A molecule composed of too few monomer units for it to be classified as a polymer but more than in a dimer trimer tetramer etc Oligonucleotide (Section 28 6) A polynucleotide containing a relatively small number of bases Oligosaccharide (Section 25 1) A carbohydrate that gives three to ten monosacchandes on hydrolysis Optical activity (Section 7 4) Ability of a substance to rotate the plane of polanzed light To be optically active a sub stance must be chiral and one enantiomer must be present in excess of the other... 

Inhibitors slow or stop polymerization by reacting with the initiator or the growing polymer chain. The free radical formed from an inhibitor must be sufficiently unreactive that it does not function as a chain-transfer agent and begin another growing chain. Benzoquinone is a typical free-radical chain inhibitor. The resonance-stabilized free radical usually dimerizes or disproportionates to produce inert products and end the chain process. 

The cyclization of a polymer that has already grown through the dimer or trimer stage is also insignificant. 

The polymer described in the last problem is commercially called poly (phenylene oxide), which is not a proper name for a molecule with this structure. Propose a more correct name. Use the results of the last problem to criticize or defend the following proposition The experimental data for dimer polymerization can be understood if it is assumed that one molecule of water and one molecule of monomer may split out in the condensation step. Steps involving incorporation of the monomer itself (with only water split out) also occur. 

The observed molecular weight suggests that this polymer associates into a dimer in CHCI3, but that this aggregation is effectively blocked by small amounts of DMF. The particle lengths are not quite in the 2 1 ratio indicative of end-to-end association, but the increase in length is sufficiently large to make such a mechanism worthy of additional study. 

In the commercial Gorham process (2), the extremely reactive PX is conveniendy generated by the thermal cleavage of its stable dimer, Vo-di- -xyljIene (DPX), a [2.2]paracyclophane [1633-22-3] (3). In many instances, substituents attached to the paracyclophane framework are carried through the process unchanged, ultimately becorning substituents of the polymer in the coating. 

Only one exception to the clean production of two monomer molecules from the pyrolysis of dimer has been noted. When a-hydroxydi-Zvxyljlene (9) is subjected to the Gorham process, no polymer is formed, and the 16-carbon aldehyde (10) is the principal product in its stead, isolated in greater than 90% yield. This transformation indicates that, at least in this case, the cleavage of dimer proceeds in stepwise fashion rather than by a concerted process in which both methylene—methylene bonds are broken at the same time. This is consistent with the predictions of Woodward and Hoffmann from orbital symmetry considerations for such [6 + 6] cycloreversion reactions in the ground state (5). 

Manufacture. For the commercial production of DPXN (di-/)-xylylene) (3), two principal synthetic routes have been used the direct pyrolysis of -xylene (4, X = Y = H) and the 1,6-Hofmaim elimination of ammonium (HNR3 ) from a quaternary ammonium hydroxide (4, X = H, Y = NR3 ). Most of the routes to DPX share a common strategy PX is generated at a controlled rate in a dilute medium, so that its conversion to dimer is favored over the conversion to polymer. The polymer by-product is of no value because it can neither be recycled nor processed into a commercially useful form. Its formation is minimised by careful attention to process engineering. The chemistry of the direct pyrolysis route is shown in equation 1 ... 

To an experienced operator trained in the handling of industrial chemicals, the dimers present Httle cause for concern in handling or storage. The finished polymer coating presents even less of a health problem contact with the reactive monomer is unlikely. In the ancillary operations, such as cleaning or adhesion promotion, the operator must observe suitable precautions. Before using the process chemicals, operators must read and understand the current Material Safety Data Sheets, which are available from the manufacturers. 

Acryhc esters dimerize to give the 2-methylene glutaric acid esters catalyzed by tertiary organic phosphines (37) or organic phosphorous triamides, phosphonous diamides, or phosphinous amides (38). Yields of 75—80% dimer, together with 15—20% trimer, are obtained. Reaction conditions can be varied to obtain high yields of trimer, tetramer, and other polymers. 

The extract is vacuum-distilled ia the solvent recovery column, which is operated at low bottom temperatures to minimise the formation of polymer and dimer and is designed to provide acryUc acid-free overheads for recycle as the extraction solvent. A small aqueous phase in the overheads is mixed with the raffinate from the extraction step. This aqueous material is stripped before disposal both to recover extraction solvent values and minimise waste organic disposal loads. 

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