Jeffamines

Jean Marie Farina Jeffamines Jeffrey s rule Jellies... 

The ATPEs have a poly(propylene oxide) backbone widi amine endgroups, as shown in Scheme 4.4. There are several routes to such materials,25 but the only one in current commercial production is die direct amination of polyether polyols. A line of uretiiane-grade ATPEs is made by Huntsman under the tradename Jeffamine. Mono-, di-, and trifunctional products are available in molecular weights up to 5000 g/m. 

Catalyst Study. Equivalent amounts of p-phenylenebis(4,4-dimethyl-2-oxazol1n-5-one ) (2) and Jeffamine D-2000 (polyoxypropylenediamine from Texaco Chemical Co., amine equiv. weight 1023) were mixed with 5 mole % of the desired catalyst. The stirred mixture was heated at 240°C under argon for 30 minutes, then an additional 1.5 hours under vacuum (<1 torr) and collected. The amount of cyclization was estimated by 1H-NMR in CDC 13 by comparison of the Integrated intensities of the absorptions due to the gem-dimethyl substituents. These absorptions appeared at 1.39 ppm in the cyclic form and at 1.73 ppm in the open-chain form of the polymer (see Scheme 4). Results are listed in Table I. 

PEG-Amine Derivative (Jeffamine Series from Texaco Various Polymer Lengths Available)... 

Abstract PAMAM types polyether based dendrimers were synthesized from three branched Jeffamines . Synthesized compounds bears metylester/ferf-butylester, caiboxylic acid or amine groups. In the synthesis iterative Micheal type of reaction paths were followed. Catalytic properties of the molecules were studied in homogenous phase. 

Keywords Catalysis, dendrimer, dendritic Jeffamines, Micheal addition, PAMAM... 

Methylacrylate and ethylenediamine were obtained from the Merck. Jeffamine T-3000 was purchased from Texaco Chemical Company. Other chemicals were used as obtained from the Fluka without further purification unless otherwise noted. Solvents were dried and distilled according to literature procedures prior to use. Reactions were controlled by thin layer chromatography (TLC) on silica gel 60 F254 and spots were detected either by UV-visible light or by charging with vapor. 

Scheme 14.1 Aciylation of Jeffamine and corresponding acid (Jeff-(COjMe) and Jeff-(COjH) )...

We have described a straightforward method for the synthesis of three directional ester, carboxylic acid and amine terminated Dendritic molecules from Jeffamine all of the products were soluble in most of the organic solvents, In addition,... 

General Procedure A (esterification of amine) 1 A 50 wt% methanol solution of methyl acrylate (17 g, 0.2 mol) was added to the methanolic solution of Jeffamine T-3000 (100 g, 0.033 mol). This reaction was allowed to stir at room temperature under a nitrogen atmosphere for 48 h. The reaction was then heated to 50°C for 1 h. methanol and excess methyl aerylate were removed by rotary evaporator. After the dialysis using membrane filter with a MWCO of 3 D in methanol, the product was obtained as a yellow viscous oil (6 g, 98%). H NMR (CDCl, 5),... 

In an extension of this work, the reuse of the polymeric catalyst was addressed and several new PE-poly(alkene) glycol copolymers were prepared [68]. Commercially available oxidized polyethylene (CO2H terminated, both high and low molecular weight) was converted to the acid chloride and reacted with Jeffamine D or Jeffamine EDR, and subsequently converted to the tributylammonium bromide salt with butyl bromide. These new quaternary salts were shown to catalyze the nucleophihc substitution of 1,6-dibromohexane with sodium cyanide or sodium iodide. While none of the polymeric quaternary salts catalyzed the reaction as well as tetrabutylammonium bromide, the temperature-dependent solubility of the polymers allowed removal of the polymer by simple filtration. 

Figure 13. Photon emission from the tensile loading of model unidirectional epoxy composites made with (a) unsized and (b) sized E-glass fibers in Epon 828/Jeffamine. (Reproduced with permission from Ref. 33 Copyright 1988 Elsevier Applied Science.) (Continued on next page.)...

A reactor was charged with 96% active bis(perfluorobutylsulfonyl)imine (1.26 mol) dissolved in water (760 g) and then treated with Jeffamine XJT-500 (0.66 mol) at 70°C over 30 minutes. The mixture was stirred an additional 15 minutes and the pH adjusted to 7-8. The solution was then concentrated under reduced pressure and 1042 grams of product isolated as an amber honey-like liquid. 

TABLE 1. Selected Polypropylene Ether Ammonium Salts Prepared Using Jeffamine Polyether Amines and Bis(perfluoroalkylsulfonyl)imine... 

Entry Jeffamine Molecular Weight (Da) Anion Yield (%)... 

Jeffamines are materials that contain polypropylene glycol, poly(ethylene oxide-h-propylene oxide), or poly(propylene oxide-ethylene oxide-h-propylene oxide), which contain an amine terminus. 

Attempts have also been undertaken to improve the processability of PMR imide resins through molecular weight adjustments and exchange of the monomers employed. LARC 160 as an example here Jeffamine AP22, a eutectic blend of MDA type amines, was used as a polyamine instead of the crystalline MDA. This modification provided a quasi melt processable PMR resin (15). Other modifications were studied with the aim of improving the thermal oxidative stability by using hexafluoroisopropylidene dipthalic anhydride as a monomer (16). 

A solventless PMR resin became known under the designation LARC 160 (15), which could be processed as a hot melt. An exchange of MDA in PMR-15 with a liquid isomeric mixture of di- and trifunctional amines (Jeffamine 22) provided a mixture of monomeric reactants which was tacky at room temperature. In the presence of 3% methanol the resin could be processed via a hot melt process. Unfortunately, the cured resin was inferior with respect to thermal oxidative stability in comparison to PMR-15. 

The reaction occurs rapidly at alkaline pH (7—10), with higher pH values resulting in better yields due to faster Schiff base formation. To ensure complete conversion of available aldehydes to amines, add the ammonia or diamine compound to the reaction in at least a 10-fold molar excess over the expected number of formyl groups present, Diamines that are commonly used for this process include ethylene diamine, diamino-dipropylamine (3,3 -iminobispropylamine), 1,6-diaminohexane, and the Jeffamine derivative EDR-148 containing a hydrophilic, 10-atom chain (Texaco Chemical Co.). 

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