Imine polymerization

Figure 2. Proposed reaction mechanism for (a) insertion, (b) chain termination and (c) chain branching in the case of the Brookhart Ni-bis-imine polymerization catalyst. Large bulky substituents have been removed for clarity...

To date these have not been very important as active centres of polymerizations, mainly because of the limited number of conventional monomer types suitable for building such a centre. Nitrogen cations are an exception. Cyclic imines polymerize on centres [148, 149]... 

Similarly, ethylene imine polymerizes quite readily in the presence of cationic initiators (see Eq. 2.46). 

Alkanolamines [ALKANOLAMINES - ALKANOLAMINES FROM OLEFIN OXIDES AND AL ONIA] (Vol 2) -polymerization of [IMINES, CYCLIC] (Vol 14)... 

Polyamines can also be made by reaction of ethylene dichloride with amines (18). Products of this type are sometimes formed as by-products in the manufacture of amines. A third type of polyamine is polyethyleneimine [9002-98-6] which can be made by several routes the most frequently used method is the polymeriza tion of azitidine [151 -56 ] (18,26). The process can be adjusted to vary the amount of branching (see Imines, cyclic). Polyamines are considerably lower in molecular weight compared to acrylamide polymers, and therefore their solution viscosities are much lower. They are sold commercially as viscous solutions containing 1—20% polymer, and also any by-product salts from the polymerization reaction. The charge on polyamines depends on the pH of the medium. They can be quaternized to make their charge independent of pH (18). 

The first-order decomposition rates of alkyl peroxycarbamates are strongly influenced by stmcture, eg, electron-donating substituents on nitrogen increase the rate of decomposition, and some substituents increase sensitivity to induced decomposition (20). Alkyl peroxycarbamates have been used to initiate vinyl monomer polymerizations and to cure mbbers (244). They Hberate iodine quantitatively from hydriodic acid solutions. Decomposition products include carbon dioxide, hydrazo and azo compounds, amines, imines, and O-alkyUiydroxylarnines. Many peroxycarbamates are stable at ca 20°C but decompose rapidly and sometimes violently above 80°C (20,44). 

FIGURE 2 Polymers that can be derived firom L-serine. (a) Poly-(serine ester) was obtained by ring opening polymerization of N-protected serine-p-lactones (19). (b) Poly(serine imine) has appar-... 

Highly c/s-selectivity and low molecular weight distribution polymerization of l -butadiene with cobalt(II) pyridyl bis(imine) complexes in the presence of ethylaluminum sesquischloride effect of methyl position in the ligand... 

Table 1. Solution polymerization results for butadiene usir cobalt(II) pyridyl bis(imine) complexes. Polymerization conditions [l,3-butadiaie]= 1 mol/L [Cal.] = 2.00 x 10" mol/L ...

The results presented above indicate that the previously unknown head-to-tail polymerization is the major reaction product of the iminium methide species. To investigate the generality of this reaction, we next studied a neutral ene-imine species shown in Scheme 7.9.48 As illustrated in this scheme, the generation of this reactive species requires quinone reduction followed by elimination of acetic acid. The ene-imine is structurally related to the methyleneindolenine reactive species that is a metabolic oxidation product of 3-methylindole (Scheme 7.9).57 59... 

The earliest polymeric cationic aftertreatments stemmed from the development of crease-resist finishes for cellulosic fibres. One such, promoted specifically for its colour fastness improvements when applied as an aftertreatment to direct dyeings, was a condensation product of formaldehyde with dicyandiamide (Scheme 10.82). Many similar compounds followed, such as condensation products of formaldehyde with melamine (10.212), polyethylene imine) with cyanuric chloride (10.213) and alkyl chlorides with polyethylene imine) (10.214 R = alkyl). 

Symmetric triblock copolymers of the ABA type, where B was PTHF and A poly(2-methyl-2-oxazoline), PMeOx, were prepared by cationic polymerization with trifluoromethanesulfonic anhydride as a difunctional initiator [58]. Subsequent hydrolysis of the PMeOx blocks with HC1 in a methanol/ water mixture resulted in the formation of the corresponding polyethylen-imine blocks (Scheme 20). Samples with relatively low molecular weight distributions were obtained. 

In this contribution, we describe the discovery and application of phenoxy-imine ligated early transition metal complexes (FI catalysts) for olefin polymerization, including the concept behind our catalyst design, the discovery and the polymerization behavior of FI catalysts, and their applications to new polyolefinic materials. 

Among the highly active catalysts introduced above, bis(phenoxy-imine) early transition metal complexes (Fig. 9) in particular show strikingly high activities for the polymerization of ethylene [14, 51-54]. 

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