LIST OF REACTANTS

and PRODUCTS

FOR PROCESS

DESCRIPTION Material Designation N1-(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 minohexyl)-1,6-hexa

nedia sodium chloride
FORMATION

OFLINEAR

DTTHIOCARBAMATES

FROM OLIGOMERIC

POLYAMINES

STEP 1: Inthe firststep

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. Tothe reaction

vessel 2-(chloromethyl)-oxirane (B) (commonly

referred to as epichlorohyrin), denoted as REACTANT

B in the scheme

below is added

over4 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 bothalkylate 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, wheren=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 BThese intermediate

oligomers

are not isolated

and are used

in total in STEP

2'

STEP 2: To the molten (gg"c)

intermediate

oligomers

and unreactedN1-(6-aminohexyl) 1,6-hexanediamine (A) formed in Step 1 of the process is added sufficient

water (G),

as a solvent,

to yielda 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

formedfrom the reaction of 2-(chloromethyl)-oxirane with the starting

amine, totally

form the sodium saltof the dithiocarbamate

formedby 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 pointthe reactor is sealed

and purged

with Nitrogen

gas such that 2 to 3 volumes

of headspace in the reactor

are replaced

by Nitrogen.

This isto 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 pHof 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 wasdissolved

in 50 ml of 50%

isopropanol

in water. To thissolution 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.After30 minutes of stirring

the solution

was titrated with 0'1N HCI and required

0.7 mls of titrant

to yield a pHof 3.8. This

yields an amine

value (AV2) for the solution

of 20.Thus the tertiary

amine content can be calculated

as AV2 /AYL=% tertiaryamine

content or approximately

3.So/o. This dataestablishes

that the oligomer

forming the backbone

of the NC

is composed

almost entirely primary and secondary

amines. Thatis, the oligomer

isalmost

entirely linear in nature.