*3.3.1. GC/MS analysis*

De Brabander‐van der Berg and Meijer reported successful hydrogenation over Raney cobalt catalyst in water under H2 pressure of 30–70 bar. Under these conditions no side products were

The cross‐linking agents (N,N,N‐tri(3‐aminopropyl)amine and (N,N,N′,N′‐tetra(3‐amino‐ propyl)ethylenediamines were obtained in the catalytic hydrogenation process of appropri‐

Preparation of N,N,N‐tricyanoethylamine (TCA) and N,N,N′,N′‐tetracyanoethyl‐1,2‐ethyle‐ nediamine (TCED) was performed by means of bimolecular Michael addition of acryloni‐ trile to ammonia and ethylenediamine, respectively. The exotermic reaction of poly(nitriles) intermediates TCA and TCED starts with an addition of excessive acrylonitrile to the appro‐

The poly(nitriles) used for hydrogenation process were synthesized in the reaction of 30% water solution of ammonia or 1,2‐ethylenediamine containing 1,4‐dioxane and ionic liquid with an excessive amount of acrylonitrile. When the reaction was completed at 60°C, poly(ni‐ triles) were separated by means of a separatory funnel and dried over magnesium sulfate in

The synthesized poly(nitriles) are the substrates in the hydrogenation reaction to obtain the primary poly(amines). This reaction was carried out in the presence of the Ni catalyst in the high‐pressure autoclave giving the final product of the polyamines—(N,N,N‐tri(3‐amino‐ propyl)amine) (TAA) or (N,N,N′,N′‐tetra(3‐aminopropyl)‐ethylenediamine)) (TAED) with

Poly(nitriles) used for hydrogenation reaction were obtained in a cyanoethylation process, as

**Figure 5.** Cyanoethylation of ammonia and 1,2 ethylenediamine to N,N,N tricyanoethylamine (TCA) — 3 and N,N,N',N' tetracyanoethylo 1,2 ethylenediamine (TCED) 4 followed by their hydrogenation reaction gives (N,N,N tri(3 aminopropyl)amine) (TAA) — 5 and (N,N,N',N' tetra(3 aminopropyl)ethylenediamine)) (TAED) — 6, respectively.

The hydrogenation reactions were carried out at 135°C, under 10 bars for 6 h. In the case of

In case of hydrogenation of TCA for 0.14 mol of nitrile, 0.42 mol of H2 is needed for total conversion of nitrile groups into primary amino groups. It was determined that to achieve full

TAA synthesis, yield of this reaction reached 85.7%, while for TAED exceeded 82%.

obtained and 99.5% selectivity level per conversion was achieved [31].

238 New Advances in Hydrogenation Processes - Fundamentals and Applications

ate poly(nitriles) in the presence of modified silica support Ni catalyst.

priate amine under ambient conditions.

order to remove any traces of water.

82.0% and 88.0% yields, respectively.

shown in **Figure 5** without purification procedures.

GC/MS analyses of the branched polyamines were done by use of a gas chromatograph HP 6890 Series GC System (Hewlett‐Packard) equipped with HP 5973 Network quadrupole mass selective spectrometric detector (Agilent Technologies) in a similar way as it was described in Section 2.3.1.

Hydrogenation process of TCED leads to the formation of N,N,N′‐triaminepropyl‐1,2‐ethyl‐ enediamine with retention time *tr* =19.61 min and N,N,N′,N′‐tetraaminepropyl‐1,2‐ethylene‐ diamine (TAED) with *tr* = 23.60 min and small amounts of undesired by‐products, which peaks are shown in **Figure 7**. In this reaction mixtures, besides the main products—compo‐ nents B and C, n‐propylamine (component A) with *tr* =2.31 min is present. The mechanism of its formation probably is either by hydrogenolysis or retro‐Michael reaction in which main products decomposes into molecules with lower molecular weights.
