Amine bearing polymers

Polymers were used to test the intermediacy of a phosphorylated compound in phosphorylations observed during base-promoted decomposition of /3-halo phosphonate (Conant-Swan reaction) (Rebek et al., 1977,1978). Polymer-bound jS-chlorophosphonate was prepared and decomposed in the presence of an amine-bearing polymer of different bead size. It was shown that phosphorylation of the amine-bearing polymer occurred, indicating the intermediacy in solution of a phosphorylating species. 

There are four different chemical reactions that have been used to crosslink polymers with peptide sequences (Fig. 6.8) (i) amide bond formation (ii) Michael-type addition (iii) Huisgen cycloaddition (click reaction) and (iv) radical polymerisation. The amide bond formation follows typical solid phase peptide synthesis (SPPS) protocols and does not require functionalisation of the termini of the peptide sequence. Fluorenyhnethoxycarbonyl (Fmoc) protection of the N-terminus allows attachment of the peptide sequence to an amine-bearing polymer. After removal of the Fmoc group, the amine-terminated peptide-polymer conjugate can be reacted with a second polymer bearing carboxylic acid functionalities using the same coupling chemistry (Maier et al, 2011). For Michael-type additions the peptide... 

Imidization is a very well known amine/anhydride reaction in organic chemistry. It is a spontaneous reaction, does not require a molecular catalyst and has the advantage to take place also in the absence of solvent at high melt temperature. Examples of reactive blends making use of an imidization reaction are listed in Table 3.1. Amine bearing polymers... 

The palladium-catalyzed amination reaction with a monofunctional primary amine 167 effects i / -diarylation to afford the tertiary amine polymers 168. Hence, polycondensation of 167 with bifunctional arylene dihalides leads to 168 (Equation (81)). Polycondensation of a primary amine bearing an azobenzene moiety with dibromides in the presence of Pd2(dba)3 (2.5mol%)- Bu3P (P/Pd = 3 l) and NaO Bu at 100°G for 24h in toluene gives 168 in 81-93% yields, as reported by Kanbara. 

Continuing attention has been paid to the synthesis of amine-bearing monomers, e.g. N-(4-anilinophenyl (methacrylamide, used for the synthesis of the ter-polymer 13, and other monomers containing PD or PT moieties [8]. Copolymers of the acryloyl-PT with conventional acrylates were proposed for optical lenses and hydrogels [118]. Formation of a polymer-bound amine via copolymerization of butadiene with acrylonitrile in the presence of N-phenyl-A -alkoxy-BQDI was mentioned. 

Mannose can interact specifically with macrophages and dendritic cells via surface mannose receptors involved in endocytosis and phagocytosis [61]. A mannose moiety can be introduced onto chitosan or chitosan-g-polyethyleneimine (PEI) molecules by a thiourea reaction between the isothiocyanate group and the amine groups (Eig. 6) [62, 63]. The mannose-bearing polymers show enhanced macrophage-specific bioactivity both as a vaccine and as a gene delivery system. 

The structure of the poly(N-vinylpyrrolidone-co-vinyl amine) bearing aminophosphonate groups was proved by and P NMR spectroscopy. This polymer is interesting because it has its own biological activity. 

Material properties of olefin metathesis polymers made by thermal (ROMP) or photoinduced (PROMP) polymerization with ruthenium (Il)-salts and the later developed ruthenium-phosphines as catalysts are described. The low oxidative stability was improved by copolymerization with so-called "build-in" antioxidants (AOs), i.e. hindered phenols or aromatic amines bearing 2-norbornene units. 

In the manufacture of highly resident flexible foams and thermoset RIM elastomers, graft or polymer polyols are used. Graft polyols are dispersions of free-radical-polymerized mixtures of acrylonitrile and styrene partially grafted to a polyol. Polymer polyols are available from BASF, Dow, and Union Carbide. In situ polyaddition reaction of isocyanates with amines in a polyol substrate produces PHD (polyhamstoff dispersion) polyols, which are marketed by Bayer (21). In addition, blending of polyether polyols with diethanolamine, followed by reaction with TDI, also affords a urethane/urea dispersion. The polymer or PHD-type polyols increase the load bearing properties and stiffness of flexible foams. Interreactive dispersion polyols are also used in RIM appHcations where elastomers of high modulus, low thermal coefficient of expansion, and improved paintabiUty are needed. 

The polymers initiated by BP amines were found to contain about one amino end group per molecular chain. It is reasonable to consider that the combination of BP and such polymers will initiate further polymerization of vinyl monomers. We investigated the photopolymerization of MMA with BP-PMMA bearing an anilino end group as the initiation system and found an increase of the molecular weight from GPC and viscometrical measurement [91]. This system can also initiate the photopolymerization of AN to form a block copolymer, which was characterized by GPC, elemental analysis, and IR spectra. The mechanism proposed is as follows ... 

Finally, Lecomte and coworkers reported the synthesis of mikto-arm star-shaped aliphatic polyesters by implementing a strategy based on click chemistry (Fig. 36) [162]. Firstly, the polymerization of sCL was initiated by a diol bearing an alkyne function. The chain-ends were protected from any further undesired reaction by the esterification reaction with acetyl chloride. The alkyne was then reacted with 3-azidopropan-l-ol. The hydroxyl function located at the middle of the chain was then used to initiate the ROP of sCL and y-bromo-s-caprolactone. Finally, pendant bromides were reacted successfully with sodium azide and then with N, N-dimethylprop-2-yn-l-amine to obtain pendant amines. Under acidic conditions, pendant amines were protonated and the polymer turned out to exhibit amphiphilic properties. 

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