Poly triazines

Poly(triazines) are being considered for use as compression molding materials, especially for laminates. 

Poly(triazine) G2 PEG Paclitaxel Ester or ester- Cancer No Yes Yes 349... 

Figure 1 LOI of intumescent systems based on various phosphates A - ammonium polyphosphate + poly(triazine-piperazine) B - ethylenediamine phosphate + melamine C - melamine phosphate + dipentaerythritol.

The formulation of more recent APP-based systems also seems to be based on phosphorus-nitrogen synergism. Co-additives are polymeric in nature such as poly(triazine-piperazine) materials, essentially substituted melamine rings linked by piperazine groups, and poly(ethylene-urea-formaldehyde) condensates. The sequence of reactions leading to char formation in these systems is poorly understood. It is likely that both water and ammonia are evolved at certain stages, some phosphorus and probably some nitrogen remain incorporated in the char structure, and some phosphorus ends up as polyphosphoric acid. 

Poly(triazine-2.4 diyl-perfluoroethylidene-block-oxyperfluoropropylene) SEC, porous silica 1765... 

The most spectacular results with temperature-programmed LC have been obtained for some notoriously difficult polymeric additives. Characterisation of the oligomeric HALS stabiliser poly [[6-[(l,l,3,3-te-tramethylbutyl) amino]-l,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]-l,6-hexanediyl [(2,2,6,6-tetramethyl-4-piperidyl)imino]] (I) (Figure 4.12) is difficult for several reasons it has a broad MWD, may contain isomers, and has several amino groups that promote almost irreversible adsorption to silica based column packings in LC. 

Figure 4.12 HAS compound with IUPAC name poly[[6-[(l,l,3,3-tetramethylbutyl)amino]-l,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]-l,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidyl) imino]]...

Joyce J, Cook J, Chabot D et al (2006) Immunogenicity and protective efficacy of Bacillus anthracis poly-y-D-glutamic acid capsule covalently coupled to a protein carrier using a novel triazine-based conjugation strategy. J Biol Chem 281 4831 -843... 

Polymeric materials invented by CDT are conjugated homo- or copolymers. Examples are poly(arylenevinylene)s, [ArCRy CR2L] , polymers with triarylamine and triazine groups (Figure 11.17), and fused thiophenes as structural repeating units (Figure 11.18). 

Figure 5.17 Noncovalent cross-linking strategies of cyanuric acid functionalized poly-CA to form (a) poly-CA-triazine by using a diaminotriazine cross-linking agent or (b) poly-CA-wedge by using an isophthalamide cross-linking agent.

Figure 5.18 Cross-linking profile of poly-CA using the triazine-based cross-linking agent. Filled symbols denote the elastic modulus (G ) whereas empty symbols denote the loss modulus (G") at a strain value of 0.1. The percentage of the triazine-based cross-linking agent is based on the cyanuric acid groups attached to the polymer.

Namazi H, Adeli M. Solution properties of dendritic triazine/poly(ethylene glycol)/dendritic triazine block copolymers. J Polym Sci Part A Polym Chem 2005 43 28-41. 

Electron-deficient heteroaromatic systems such as 1,2,4-triazines and 1,2,4,5-tetrazines easily undergo inverse electron demand Diels-Alder (lEDDA) reactions. 1,2-Diazines are less reactive, but pyridazines and phthalazines with strong electron-withdrawing substituents are sufficiently reactive to react as electron-deficient diazadienes with electron-rich dienophiles. Several examples have been discussed in CHEC-II(1996) <1996CHEC-II(6)1>. This lEDDA reaction followed by a retro-Diels-Alder loss of N2 remains a very powerful tool for the synthesis of (poly)cyclic compounds. 

Because of its chemical inertness, no direct way of curing poly(thiocarbonyl fluoride) has been found. However, creep has been reduced and strength at elevated temperatures improved by milling into the polymer a free-radical generator, such as dicumyl peroxide or azobisisobutyronitrile, and a free-radical acceptor, such as N,N -m-phenylenebismaleimide or triacryloylhexahydro-s-triazine, and curing with heat and pressure (65). A better method is to mill in divinylbenzene and a small amount of benzoyl peroxide and cure with heat and pressure (66). The divinylbenzene forms a crosslinked matrix that mechanically traps poly(thio-carbonyl fluoride) molecules. Since the elastomer is in effect filled with poly(di-vinyl benzene), the final composition is less resilient than untreated poly(thio-carbonyl fluoride). 

Inverse electron demand Diels-Alder/retro-Diels-Alder-type reactions, of di- and especially poly-azines with electron-rich dienophiles, interconvert six-membered rings. 1,2,4-Triazines react with enamines and enol ethers to give pyridines (Scheme 76) (CHEC-n(5)242). 

The first work in this field was probably that of Piletsky et al. [84] that described a competitive FILA for the analysis of triazine using the fluorescent derivative 5-[(4,6-dichlorotriazin-2-yl)amino]fluorescein. The fluorescence of the supernatant after incubation was proportional to the triazine concentration and the assay was selective to triazine over atrazine and simazine. The same fluorescent triazine derivative was applied to competitive assays using atrazine-imprinted films [70]. To this end an oxidative polymerization was performed in the presence of the template, the monomer(s) 3-thiopheneboronic acid (TBA) or mixtures of 3-amino-phenylboronic acid (APBA) and TBA (10 1) in ethanol-water (1 1 v/v) where the template is more soluble. The polymers were grafted onto the surface of polystyrene microplates. The poly-TBA polymers yielded a detection limit of 8 pM atrazine whereas for the poly-TBA-APBA plates it was lowered to 0.7 pM after 5 h of incubation. However, a 10-20% decrease in the polymer affinity was observed after 2 months. 

Here we report the use of a readily prepared polymer immobilised TEMPO as a catalyst for alcohol oxidations.15 It was derived from a commercially available oligomeric, sterically hindered amine, poly[[6-[(l,l,3,3-tetramethylbutyl)amino]-l,3,5-triazine-2,4-diyl] [2,2,6,6-teramethyl-4-piperidinyl)-imino]-1,6-hexane-diyl[(2,2,6,6-tetramethyl-4-piperidinylimino]], better known as Chimassorb 944 (MW 3000 see figure 3 for structure). This compound is used as an antioxidant and a light stabiliser for plastics. It contributes significantly to the long-term heat stability of polyolefins and has broad approval for use in polyolefin food packaging.16... 

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