Polypropylene amines

In a way related are the complexes formed by Hg salts and multicrown dendrimers of different generations (dendrimers with a polypropylene amine interior of different volume and benzo[15]-crown-5 ether periphery), studied by extraction methods using radioactive 203Hg2+.210 Up to 12 Hg2+ ions were found to be bound per dendrimer molecule, obviously in the amine-dominated interior, not in the crown-ether periphery. 

Vogtle F, Gestermann S, Kauffmann C et al (2000) Coordination of C02+ ions in the interior of polypropylene amine) dendrimers containing fluorescent dansyl units in the periphery. J Am Chem Soc 122 10389-10404... 

Fe2(III,III)2+ states. By considering that organometallic dendrimers based on conjugated ferrocene units are of special importance since mixed-valence states have interesting electrical, redox, and magnetic properties, recently three generations of polypropylene amine) dendrimers, decorated at their periphery with 4, 8, and 16 (compound 6, Fig. 6.6a) BFc units, respectively, have been synthesized and the electrochemical behavior of the dendrimers complexed with (3-cyclodextrins ([3-CD) and adsorbed at self-assembled monolayers (SAMs) of heptathioether-functionalized [3-CD on gold (molecular printboard) has been studied.40... 

The first family of polycationic cobaltocenium dendrimers reported in the literature is constituted by four generations of the diaminobutane-based polypropylene amine) dendrimers containing 4, 8, 16, and 32 (compound 7 in Fig. 6.7a) cobaltocenium peripheral units, respectively.41... 

Carbon-based sorbents are relatively new materials for the analysis of noble metal samples of different origin [78-84]. The separation and enrichment of palladium from water, fly ash, and road dust samples on oxidized carbon nanotubes (preconcentration factor of 165) [83] palladium from road dust samples on dithiocarbamate-coated fullerene Cso (sorption efficiency of 99.2 %) [78], and rhodium on multiwalled carbon nanotubes modified with polyacrylonitrile (preconcentration factor of 120) [80] are examples of the application of various carbon-based sorbents for extraction of noble metals from environmental samples. Sorption of Au(III) and Pd(ll) on hybrid material of multiwalled carbon nanotubes grafted with polypropylene amine dendrimers prior to their determination in food and environmental samples has recently been described [84]. Recent application of ion-imprinted polymers using various chelate complexes for SPE of noble metals such as Pt [85] and Pd [86] from environmental samples can be mentioned. Hydrophobic noble metal complexes undergo separation by extraction under cloud point extraction systems, for example, extraction of Pt, Pd, and Au with N, A-dihexyl-A -benzylthiourea-Triton X-114 from sea water and dust samples [87]. 

Behbahani, M., Gorji, T., Mahyari, M., Salarian, M., Bagheri, A., Shaabani, A. Application of polypropylene amine dendrimers (POPAM)-Grafted MWCNTs hybrid materials as a new sorbent for solid-phase extraction and trace determination of gold(III) and palladium(II) in food and environmental samples. Food Anal. Methods 7, 957-966 (2014)... 

Fig. 2. Plot of the absorbance of the molybdosilicate versus the reaction time (a) polyethylene amines, (b) polypropylene amines. Amine concentration 10 mg/L.

Polypropylene amines, poly(amidoamines) (PAMAM) and silicon dendrimers set records for the number of generations, whereas the polyacetylene dendrimer prepared by Moore et al. [6] with the formula C1398H1278 and a mass of 18079.53 holds the heavyweight championship title of pure hydrocarbons. Mullen et al. have recently published a series of aromatic hydrocarbon dendrimers consisting of phenylene-bridged benzene rings. [7] Interestingly, these species form two-dimensional planes rather than three-dimensionally extended structures. 

Co(III) and NaBH4. Iterative repetition of these two steps allows one to obtain cascade polymers , as Vogtle initially described them, but in poor yields. Optimization of Vdgtle s original inefficient synthesis by Meijer and Mulhaupt in 1993 resulted in the preparation of poly(propylenimine) dendrimers (Scheme 13.9). The high yield and degree of purity obtained in this synthesis has made these dendrimers one of the most popular architectures in dendrimer chemistry. They have also been produced on an industrial scale and can be found under different names, in particular PPI (for polypropylenimine), DAB (for diaminobutane) and POPAM (for polypropylene amine), depending on the nature of the core. 

Oligomeric hindered amine light stabilizers are effective thermal antioxidants for polypropylene. Thus 0.1% of A[,Af-bis(2,2,6,6-tetramethyl-4-piperadinyl)-l,6-hexanediamine polymer, with 2,4,6-trichloro-l,3,5-triazine and 2,4,4-trimethyl-2-pentaneainine [70624-18-9] (35) (Fig. 5), protects polypropylene multifilaments against oxidation when exposed at 120°C in a forced-air oven (22) for 47 days. 3,5-Di-/ l -butyl-4-hydroxytoluene [128-37-0] (0.1%) affords protection for only 14 days. 

Nonionic surfactants perform well in nonpolar polymers such as polyethylene and polypropylene. Examples of nonionic surfactants ate ethoxylated fatty amines, fatty diethanolamides, and mono- and diglycetides (see Amines, fatty amines Alkanolamines). Amphoteric surfactants find Httle use in plastics (134). 

In the same class of polymers, an antistat can exhibit different degrees of effectiveness. As seen in Table 6 the performance of ethoxylated oleyl amine varies among polyolefins. The data for polypropylene (PP) also shows the concentration dependence of antistats. 

The use of quenching agents in polymers is a recent development. Of particular interest are the nickel(II) chelates in polypropylene film and fibre and the even newer hindered amines which appear to combine the roles of antioxidant cmd quenching agent. 

Low surface energy substrates, such as polyethylene or polypropylene, are generally difficult to bond with adhesives. However, cyanoacrylate-based adhesives can be effectively utilized to bond polyolefins with the use of the proper primer/activa-tor on the surface. Primer materials include tertiary aliphatic and aromatic amines, trialkyl ammonium carboxylate salts, tetraalkyl ammonium salts, phosphines, and organometallic compounds, which are initiators for alkyl cyanoacrylate polymerization [33-36]. The primer is applied as a dilute solution to the polyolefin surface, solvent is allowed to evaporate, and the specimens are assembled with a small amount of the adhesive. With the use of primers, adhesive strength can be so strong that substrate failure occurs during the course of the shear tests, as shown in Fig. 11. 

Block sheiir strength of ECA on polypropylene blocks with different amines as primers. 

Table 5 Effects of Various Phenolic Modified Polypropylenes on the Properties of NBR-Polypropylene Compositions Containing Amine Terminated NBR...

Scheme 4 Reaction scheme for the formation of graft copolymer between amine terminated NBR and modified polypropylenes.

Amine salts of a-sulfonated fatty acids and esters are also used as antistatic agents. Mixtures of alkyl a-sulfo fatty acid ester diethanolamine salts and hexa-decyl stearate or butyl stearate are coated onto nylon yarn after fiber formation and before stretching [97]. Polypropylene can be made antistatic with an amine salt of a-sulfolauric acid [C10H21CH(SO3Na)COO +NH(CH2CH(OH) CH3)3] [98]. 

The history of dendrimer chemistry can be traced to the foundations laid down by Flory [34] over fifty years ago, particularly his studies concerning macro-molecular networks and branched polymers. More than two decades after Flory s initial groundwork (1978) Vogtle et al. [28] reported the synthesis and characterization of the first example of a cascade molecule. Michael-type addition of a primary amine to acrylonitrile (the linear monomer) afforded a tertiary amine with two arms. Subsequent reduction of the nitriles afforded a new diamine, which, upon repetition of this simple synthetic sequence, provided the desired tetraamine (1, Fig. 2) thus the advent of the iterative synthetic process and the construction of branched macromolecular architectures was at hand. Further growth of Vogtle s original dendrimer was impeded due to difficulties associated with nitrile reduction, which was later circumvented [35, 36]. This procedure eventually led to DSM s commercially available polypropylene imine) dendrimers. 

Similar to phenols, they can cause staining and are often used in conjunction with carbon black filled elastomers (e.g., tyres) — although carbon black itself has antioxidant capacity. For non-staining applications, e.g., polypropylene carpets, a stoically hindered amine is used, e.g.,... 

For the preparation of the triazine membranes, the entire solid support (cellulose or polypropylene membrane) was treated with a 5 m solution of the corresponding amine in l-methyl-2-pyrrolidinone (NMP) and a 1 m solution of cesium phenolate in dimethyl sulfoxide (2 p L of each at one spot) and subsequently heated in a domestic microwave oven for 3 min. After washing the support successively with... 

An 8000-member library of trisamino- and aminooxy-l,3,5-triazines has been prepared by use of highly effective, microwave-assisted nucleophilic substitution of polypropylene (PP) or cellulose membrane-bound monochlorotriazines. The key step relied on the microwave-promoted substitution of the chlorine atom in monochlorotriazines (Scheme 12.7) [35]. Whereas the conventional procedure required relatively harsh conditions such as 80 °C for 5 h or very long reaction times (4 days), all substitution reactions were found to proceed within 6 min, with both amines and solutions of cesium salts of phenols, and use of microwave irradiation in a domestic oven under atmospheric reaction conditions. The reactions were conducted by applying a SPOT-synthesis technique [36] on 18 x 26 cm cellulose membranes leading to a spatially addressed parallel assembly of the desired triazines after cleavage with TFA vapor. This concept was later also extended to other halogenated heterocycles, such as 2,4,6-trichloropyrimidine, 4,6-dichloro-5-nitropyrimidine, and 2,6,8-trichloro-7-methylpurine, and applied to the synthesis of macrocyclic peptidomimetics [37]. 

ArgoGel-MB-CHO resin (366 mg, 0.42mmol/g substitution) was placed into an Ace pressure tube (note 5). Trimethyl orthoformate (TMOF 5 mL) was added to the flask along with the primary amine (10 equiv.). The tube was capped and heated for 2h at 70°C in a rotating oven (note 6), and cooled. The TMOF solution was removed with the use of a filtration cannula, and the entire process was repeated. The resin was washed with TMOF (5 mL, lx) and anhydrous methanol (5 mL, 3 x) Anhydrous methanol (5 mL) was added to the resin, followed by the addition of sodium borohydride (133 mg, 20 equiv.). After vigorous gas evolution had ceased, the tube was capped and agitated for 8 h at room temperature. The resin was then transferred to a polypropylene reaction vessel and washed with methanol (5mL, 3 x), methanol water (1 1, 5mL, 3 x), DMF water (1 1, 5mL, 3 x), DMF (5mL, 3 x), and methylene chloride (5 mL, 3 x). 

Our library synthesis was carried out with a set of 27 tube-shaped solid phase synthesis support, called MicroTubes. These supports are prepared by radiation grafting of polystyrene ( — 350 pmol) onto polypropylene tubes, chemically functionalizing the polystyrene with aminomethyl groups to afford about 55 imol of amine per tube, inserting a reusable Rf ID tag into each tube, and heat-sealing the tube ends to prevent loss of the tag. The chemical conversion of all 36 aminomethyl tubes was carried out simultaneously using standard procedures with rink amide linker, each with —46 pmol of available amine per tube.1 2... 

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