LIST OF REACTANTS and PRODUCTS FOR PROCESS DESCRIPTION

Material

Designation

N 1-(6-amin )-1,6-hexanediamine

(2-cholormethyl)-oxira ne

intermediate oligameric polya mine

alkvlated N1-(6-amino )-1,6-hexanediamine residue

2-hydroxypropyl residue from reacted (2-chlo )-oxirane

sodium hydroxide

carbon disulfide

sodium salt of (80%) dithiocarSexylated intermediate oligameric polYamine C

sodium sa lt of dithioca rboxylated N 1-(6a m inohexyl)-1,6-hexa nedia

sodium chloride

FORMATION OF LINEAR DTTHIOCARBAMATES FROM OLIGOMERIC POLYAMINES

STEP 1:

In the first step molten N1-(5-aminohexyl) L,6-hexanediamine (A) (commonly referred to as Bishexamethylenetriamine or BHMT), denoted as REACTANT A in the scheme below, is added to a reaction

vessel. To the reaction vessel 2-(chloromethyl)-oxirane (B) (commonly referred to as epichlorohyrin),

denoted as REACTANT B in the scheme below is added over 4 hours. The chloroalkyl portion of the 2-

(chloromethyl)-oxirane as well as the epoxide function of the 2-(chloromethyl) -oxirane are both

known alkylating agents of amines. Hence one mole of the 2-(chloromethyl)-oxirane will both alkylate

the amine functions present on the N1-(6-aminohexyl) 1,6-hexanediamine to yield the intermediate

oligomeric product denoted as INTERMEDIATE PRODUCT C as shown in the reaction scheme below' For

example, the simplest intermediate oligomer product, where n=1, would be the hydrochloride salt of 1-

3 bis[6-(5-a minohexylamino) hexylam ino] propa n-2-ol'

nF4nffirclrctlcttl

nr*\-,/H\^.rHHr + *1,_ 

.RR-J -?*

I't{lsm{rmf,r.ill{} rhrn }tno|uillqr} rnf,Eilryu

ot-t

* E* -*-*-.-*-,44-*.rffir*/wE ci

ffiflffi|orglmrt Pmrb

INTERMEDIATE PRODUCT C

REACTANT A REACTANT B
These intermediate oligomers are not isolated and are used in total in STEP 2'

STEP 2:

To the molten (gg"c) intermediate oligomers and unreacted N1-(6-aminohexyl) 1,6-hexanediamine

(A) formed in Step 1 of the process is added sufficient water (G), as a solvent, to yield a So%to 55%

solution of the New Chemical (NC) at the end of the reaction. Sufficient sodium hydroxide (as 50%

aqueous solution)(F) is added to the reactor to totally neutralize the hydrochloride formed from the

reaction of 2-(chloromethyl)-oxirane with the starting amine , totally form the sodium salt of the

dithiocarbamate formed by the ensuing addition of carbon disulfide (H) to the mixture of polyamine

oligomer (C) and unreacted (A) , and in the final product contain free sodium hydroxide'

At this point the reactor is sealed and purged with Nitrogen gas such that 2 to 3 volumes of headspace

in the reactor are replaced by Nitrogen. This is to lower the oxygen content of the reaction vessel to

<L% ozas measured by Draeger tubes to eliminate any potential fire/explosion hazard with the ensuing

carbon Disulfide addition. The reactor is then sealed.

sufficient carbon disulfide (H) is slowly added to the heterogeneous liquid aqueous mass in the

reactor so as to react with available primary and secondary amine sites on the oligomeric intermediate

via a dithiocarboxylation reaction on the nucleophillic amine sites. The resulting product is shown in the

reaction scheme below. (R=hexyl).

ot-fi

Fqlr'siJr l*tl

NEW CHEMICAL (NC)
Linear character of oligomers Described in Part 1:

(2-chloromethyl)-oxirane reacted with N1-(6-aminohexyl)-1,5-hexanediamine.

12g mg (in 50 ml of 50% methanol/water) of the oligomers formed from the addition of (2-

chloromethyl)-oxirane with N1-(6-aminohexyl)-L,6-hexanediamine in the amounts and under the

conditions described in part 1 of the reaction scheme described in this PMN submission from the

addition of (2-chloromethyl)-oxirane with N1-(5-aminohexyl)-1,6-hexanediamine were titrated with 0'1

N Hcl to a pH of 3.g. This titration required 13.6 mls of titrant which yietds an amine value (AV1) of 596

for this oligomer.

In a second experiment 188 mgs of the same oligomeric material, described above was dissolved in 50

ml of 50% isopropanol in water. To this solution was added 5 ml of phenyl isothiocyanate. The resulting

material was allowed to stir for 30 minutes. Phenyl isothiocyanate is reactive with both primary and

secondary amines but unreactive with tertiary amines, and is a common laboratory method for

determining tertiary amine content. After 30 minutes of stirring the solution was titrated with 0'1N HCI

and required 0.7 mls of titrant to yield a pH of 3.8. This yields an amine value (AV2) for the solution of

20.

Thus the tertiary amine content can be calculated as AV2 /AYL=% tertiary amine content or

approximately 3.So/o. This data establishes that the oligomer forming the backbone of the NC is

composed almost entirely primary and secondary amines. That is, the oligomer is almost entirely linear

in nature.