Acrylamide functionalized oligomers

A complete listing of reactants, physical properties, and predicted and observed unsaturation equivalent weights for the telechelic (meth)acrylamide-functional oligomers is contained in Table 1. 

Figure 2. ORTEP plot of an acrylamide-functional oligomer. The large spheres denote the pol3nner residue, and the dotted lines indicate hydrogen bonding between C=0 and NH groups on respective oligomer molecules.

In the same way, Oishi et al. [256] used IEM to functionalize oligomers carrying an acid function obtained by polymerization of chiral acrylamides. Chiral polyacrylamide macromonomers were synthesized from 2-methacryloyloxyethyl isocyanate and prepolymers, i.e., poly[(S)-methyl-benzyl acrylamide] or poly(L-phenylalanine ethylester acrylamide) with a terminal carboxylic acid or hydroxyl group. Radical homopolymerizations of polyacrylamide macromonomers were carried out under different conditions to obtain the corresponding optically active polymers, as shown in Scheme 52. 

In summary, the reaction of alkenyl azlactones with amine-terminated oligomers has been found to be an excellent method for preparing the corresponding (meth)acrylamide-terminated oligomers. The reaction is characterized by a very simple synthetic sequence in which equivalent quantities of reactants are mixed at room temperature with no catalyst reactions are complete to the almost exclusion of side reactions within 16-18 hours. Furthermore, the reaction is a nucleophilic addition. This is the same manner in which nucleophiles react with isocyanates and epoxides. Indeed, this nucleophilic addition mode of reaction which involves no by-products likely accounts for the widespread use of these latter functional groups by industry. In comparison with isocyanate and epoxide, amine nucleophiles react with azlactones at controlled and predictable rates, intermediate between the very reactive isocyanate and the slow reacting epoxide. 

Functionalized alkenes are used for the cooligomerization. Phenyl-1,4,8-decatriene (104) is obtained by the Ni-catalysed 1 2 addition of styrene and butadiene [42a], Pd catalyst affords the 1 1 adduct [43], Co or Fe catalyst gives the 1 1 adducts 105 and 106 of methyl acrylate and butadiene [44,42a], The 1 1 adducts 107 and 108 are obtained by the Ru-catalyzed coupling of butadiene and acrylamide [45]. Reaction of methyl methacrylate affords the 1 2 adduct 109 with Ni—PhjP catalyst at 0°C, whereas the oligomer 110 is obtained at higher temperature [46],... 

Soluble polystyrene supports differ from the terminally functionalized PEGs and polyethylene oligomers discussed above in that the catalyst moieties are attached to polystyrene via pendant groups, the loading of which can affect both the catalyst activity and separability. One example of a simple polystyrene-supported catalyst is the polystyrene copolymer-supported quaternary ammonium salts 66 and 67 [ 103]. These copolymers can be prepared with varying ratios of the styrene unit in the copolymer - the most active catalysts had 20-40 mol% of the vinylbenzylammonium groups in the copolymers. The utility of these catalysts was studied in a variety of solvents in the addition reaction of glycidyl methacrylate and carbon dioxide (Eq. 23). Polar solvents were most useful. The necessary polymer supports for preparation of catalysts 66 and 67 were prepared from chloromethylstyrene-styrene or chloromethyl-styrene-iV,JV-dimethylacrylamide copolymers that were in turn prepared by radical polymerization of the styrene or acrylamide monomers. The catalysts were recycled up to four times with small (ca. 6%) decreases in activity - de-... 

The invention of Heath et al. relates to novel phosphonate allyl monomers, made from reaction of an unsaturated oxirane with amine- or hy-drojyl-functionalized phosphonic acids (Scheme 3.21). These monomers were copolymerized with other unsaturated species (acrylic acid, maleic acid, acrylamide, or monomer derivatives of sulfonic acid, etc), yielding phosphonate polymers or oligomers. Phosphorus-containing monomers were incorporated at a ratio of 0.1-30% and polymerized in aqueous media. The final polymers had a molecular weight of 800-30 000 g mol . With their phosphonic acids groups (free acid or salts forms), they are of particular use as oilfield scale inhibitors. 

FUNCTIONAL, TELECHELIC POLYMERS DERIVED FROM REACTIONS OF NUCLEOPHILIC OLIGOMERS AND ALKEYNL AZLACTONES, PART I TELECHELIC ACRYLAMIDES DERIVED FROM REACTIONS OF ALKEYNL AZLACTONES AND AMINE-TERMINATED OLIGOIERS ... 

Both in Chapter 10 and this chapter, we have described new techniques for the preparation of functional, telechelic oligomers and polymers based on reactions of alkenyl azlactones (Scheme 10). Nucleophilic ring-opening reactions can be utilized for the preparation of fluid acrylamides for potential use in a variety of free radical curable resin systems whereas, Michael addition leads to fluid multiazlactones which may be subsequently cured via nucleophilic addition. Further investigations concerning the chemistry and practical utility of these novel resin systems are ongoing in our laboratories. 

Oligomer and polymer additives with a primary or secondary amino group or with tertiary nitrogen able to bind water-soluble dyes containing acid groups, assortment palette of which is very wide. This function is fulfilled, e.g. by ethylene copolymers with alkyl amino-acrylates, vinylpyridine, N-vinylcarbazole and acrylamide, further acrylate copolymers, copolyamides with the derivatives of piperazine, polyaminotriazoles, polyureas and styrene-amine resins. They are added to PP before spinning in an amount up to lOwt.%... 

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