4,4 -methylene diamine

Examples of diamine chain extenders (Fig. 1.10) include 2,5-bis-(4-amino-phenylene-l,3,4-oxadiazole) (DAPO), 4,4 -diamino-dibenzyl (DAB), 2,6-diamino-pyridine (DAPy) or 4,4 -methylene-diamine (MDA). 

Another kind of 6FDA-based organo-soluble fluoro-polyimide membranes with high thermal stability was synthesized by Li and co-workers [219]. They used two types of diamines, 4,4 -methylene diamine (MDA) and 4,4 -diamino-3,3 -dimethyldiphenylmethane... 

Tetrahydroquinazolines are cyclic methylene diamines and are, therefore, readily hydrolyzed by acid to the corresponding o-aminobenzy]amines, 1,2,3,4-Tetrahydroquinazoline is a strong base (pi a 7.65), though it is not as strong as 3,4-dihydroquinazoline because of the absence of amidinium resonance in the cation. The ultraviolet spectrum is only slightly altered on protonation clearly indicating that it takes place on N-3. ... 

In addition to the Ross-Schiessler process, utilising p-CH20 and AN, the synthesis of RDX/ HMX mixts has also been reported starting with other smail molecules (Ref 7), namely, methyl-amine nitrate methylene diamine dinitrate and nitramine (NH2N02) in combination with CH20. In these reactions, the intermediate formation of Hexamine or a cyclic analog, is not necessarily established... 

Methylenediamines are readily synthesized from the reaction of secondary amines with formaldehyde. Many aliphatic amines are too basic for direct nitration without a chloride catalyst, and even then, nitrosamine formation can be a problem. Their conversion into intermediate methylenediamines before nitration is therefore a useful route to secondary nitramines. The success of these nitrolysis reactions is attributed to the inherent low basicity of the methylene-diamine nitrogens. 

Statistical copolymerization of ethylene glycol and 1,4-butanediol with dimethyl ter-ephthalate results in products with improved crystallization and processing rates compared to poly(ethylene terephthalate). Polyarylates (trade names Ardel, Arylon, Durel), copolymers of bisphenol A with iso- and terephthalate units, combine the toughness, clarity, and proce-sibility of polycarbonate with the chemical and heat resistance of poly(ethylene terephthalate). The homopolymer containing only terephthalate units is crystalline, insoluble, sometimes infusible, and difficult to process. The more useful copolymers, containing both tere- and isophthalate units, are amorphous, clear, and easy to process. Polyarylates are used in automotive and appliance hardware and printed-circuit boards. Similar considerations in the copolymerization of iso- and terephthalates with 1,4-cyclohexanedimethanol or hexa-methylene diamine yield clear, amorphous, easy-to-process copolyesters or copolyamides,... 

Ammonia is used in the production of several chemicals to make nylon adipic acid, hexa-methylene diamine, and caprolactam. It is used to treat metals in annealing, nitriding, and descaling. Ammonia is an excellent fungicide that is used to treat citric fruit. It is also used to increase the nitrogen content of crops used as feed for livestock. Ammonia dissolves readily in water to produce aqueous ammonia or ammonium hydroxide NH + 2 < > NH4+(a(i) + OH (ahydroxide ions shows that ammonia acts as a base in aqueous solution. Concentrated aqueous solutions contain 35% ammonia. Household ammonia cleaners contain between 5% and 10% ammonia. 

Fig. 93 Loss tangent versus temperature for DGEBA/HMDA (circles with bottom side black), DGEBA/tetramethylene diamine (circles with right side black) and DGEBA/dodeca-methylene diamine ( ) systems (from [65])...

C. Base-Adducts of (Ph2Si0)g[A10(0H)]4 with Poly-Methylene-Diamines H2N(CH2)nNH2 61... 

Instead of coordinating mono-hapto bases to the protons of (Ph2SiO)8[Al-0(0H)]4, we have explored the field of di-hapto bases like poly methylene diamines as possible donors. As the molecule (Ph2Si0)8[A10(0H)]4 has pairs of hydroxyl groups directed in the same direction a coordination of H2N(CH2) NH2 could either lead to an intramolecular loop or to intermolecular aggregations of molecules. This field of chemistry is actually very much expanding and we give in this review only a small out-look, essentially with the diamines 1,3-diaminopropane, 1,4-diaminobutane and 1,5-diaminopentane. 

The most striking structural element in these 1 2 adducts of (Ph2Si0)8[A10(0H)]4 with poly methylene diamines is the asymmetry in the bonding of the two diamines. In Table II always two pairs of O - N and Al-O distances are given the first pair is taken from one side of the molecule and the second from the opposite side. It is evident that although the two diamines are chemically and structurally identical and... 

Figure 10.7 Comparison of the damping peaks of tetraglycidyl methylene diamine and diamino diphenyl sulphone (TGMDA-DDS epoxy network) (O) and poly(bismaleimide) (BMI network) ( ).

The variation of the substitutes next to the amine group greatly affects the rate of reaction. A comparison between methylene diamine and MOCA shows the chlorine atoms adjacent to the amines slow the reaction rate down. This can be seen in Figure 2.31. 

DuPont. Methylene Diamine Cures Information Sheet. IF-AP-310.240 4. 

Diaminomethane or Methylene diamine (called Diaminomethan or Methylendiamin in Ger), H2N.CH2.NH2 mw 58.08, N 48i23% exists in the form of salts, ie Dihydrochloride,... 

Cramer studied the mechanism using Rh compounds [123, 124], The linear dimerization of acrylonitrile in the presence of hydrogen and a ruthenium catalyst to form 1,4-dicyano-l-butene [125-127] received much interest in industrial laboratories, mostly in Japan, so a large number of patents have been filed, in some of which palladium catalysts have also been claimed. The above compound can be hydrogenated to give the industrially important adipodinitrile and hexa-methylene diamine. 

B5hme procedure involving cleavage of JV -tetramethyl(methylene)diamine (34) with TMS-I. Qeavage of (34) with acetyl chloride in analogy to the Bdhme procedure furnishes the crystalline chloride (31), as does cleavage of methyl dimethylaminomethyl ether with methyltrichlorosilane. The trifluoroacetate (32), unlike the iodide or chloride, is a liquid and is prepared by Polonovski reaction of... 

Two in situ methods for the generation of N,A/-dimethyl(methylene)iminium salts, which are limited to reactions with enol silanes, are also available and avoid the need to handle these moisture-sensitive reagents. In the first method, iodide (30) is prepared in situ by treating methyl(methylene)diamine (34) with chloroiodomeAane (equation DMSO must be used as... 

Some comparisons between the yields of the Mannich reaction of enol silanes using in situ methods for preparation of the iminium salt and non in situ methods are shown in Table 9. Higher yields (20-30%) of P-amino ketones using in situ methods are seen in entries 2 and 4 but not in entry 1. Although a clear advantage of the in situ methods is not evident in these limited examples, in situ methods may be preferred from the standpoint of convenience. With aldehyde enol silanes (entry 3), the in situ method of Miyano et al is less practical due to elimination of the amino group, presumably caused by the strongly basic N,/V,/V, N -tetramethyl(methylene)diamine present in solution. 

The anion of phenol, in tautomeric form with the negative charge in the nucleus, attacks the carbon atom of the methylene group in the labile methylene diamine formed in reaction 15.5. 

Two in situ methods for the generation of A///-dimethyl(methylene)iminium salts, which are limited to reactions with enol silanes, are also available and avoid the need to handle these moisture-sensitive reagents. In the first method, iodide (30) is prepared in situ by treating methyl(methylene)diamine (34) with chloroiodomethane (equation 5) 36,37 DMSO must be used as solvent to achieve maximum yields. Cleavage of n-butyl dimethylaminomethyl ether (35) with TMS-I or TMS-OTf in MeCN comprises the second method (Scheme 5).38 A silyloxonium ion (36) was originally proposed as the reactive aminomethylating species, but a recent 13C NMR study of the reactions of ami-nol ethers with halosilanes in CD3CN-SO2 did detect the presence of iminium salts.39 Use of these methods in reactions with enol silanes is discussed in Section 4.1.2.2.2.iii. 

Dytek A. PuPont] 2-Methylpenta-methylene diamine epoxy curing agent also used in polyurethanes, wet strength resins, scale and corrosion inhibitors, gasoline additives, polyamide plastics, fflms, adhesives, and ii. ... 

Other Methods.—In an extension of a recently developed synthesis of phosphazenes it has been shown that tertiary phosphines react with carbon tetrachloride and methylene diamines to give diaminophosphonium salts ... 

Primary aliphatic diamines are very important intermediates in polymer industry. Tetramethylene diamine is a monomer for polyamide 4,6. Hexame-thylene diamine is used in two main industrial productions. Copolymerisation with adipic add gives rise to nylon 6,6. Reaction with phosgene leads to isocyanates which are monomers for painting industry. Methylpenta-methylene diamine is a monomer for thermoplastics (DU PONT s DYTEK). 

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