LIST OF REACTANTS and PRODUCTS FOR PROCESS DESCRIPTION

Material

Designation Material Name

A N 1-(6-a m inohexyl)-L,6-hexa ned ia m i ne

B (2-cholo rmethyl)-oxi ra ne

c intermediate oligameric polya mine

D a I kylated N 1-(6-a m inohexyl)-1,6-hexa nedia m ine resid ue

E 2-hydroxypropyl residue from react

F sodium hydroxide

G water

H carbon disulfide

sodiumsa|tof(8o%|dithiocarboxy|atedintermedi

J sod ium sa lt of dithioca rboxylated N 1-(6a m inohexyl )-1,6-hexa ned iam ine)

K sodium chloride

NONPOLYMERIC NATURE OF NCS

While the CAS Expert Inventory Service properly describes the NC as 1,6-Hexanediamine,Nl-(6-

aminohexyl)-, polymer with 2-chloromethyl)-oxirane, N-dithiocarboxy) deriv., sodium salts the EPA

definition of a polymer is a "chemical substance consisting of molecules characterized by the sequence

of one or more types of monomer units and comprising asimple weight majority of molecules

containing at least 3 monomer units or other reactant and which consist of less than a simple weight

majority of molecules of the same molecular weight. Such molecules must be distributed over a range

of molecular weights wherein differences in the molecular weight are primarily attributable to

differences in the number of monomer units". The stoichiometry of the raw materials used to

manufacture the raw materials is such that it is not possible to obtain a simple weight majority of

molecules containing 3 or more monomer units. The discussion below establishes that while the CAS

lnventroy Expert Service describes this a polymer, by EPA definition it does not qualify as a polymer.

The pages 5 and 5a in the PMN notice are therefore filled out for completeness to avoid any delays or

questions, but it is the opinion of this author that pages 4 and 4a should hold precedence.

STEP 1:

In the first step molten NL-(6-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 aswell 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) L,6-hexanediamine. The molar ratio of N1--(6-

aminohexyl) 1,6-hexanediamine to 2-(chloromethyl)-oxirane is carefully controlled such that a simple

weight percentage of components containing 3 or more N1-(6-aminohexyl) 1,6-hexanediamine residues
is not possible and ensures the formation of 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 L-3 bis[6-(6-

a minohexylamino) hexylaminol propan-2-ol.

I J it*rrF{Irflhr, ftl -tErffiroillll}

REACTANT A

{hfisn HcHffiiltBlF

REACTANT B

ht|nffil orgnrt* prffictr

INTERMEDIATE PRODUCT C

The molar ratio of N1-(6-aminohexyl) L,6-hexanediamine to 2-(chloromethyl)-oxirane ensures that

the intermediate oligomeric products do not meet the definition of a polymer. A polymer is defined as a

chemical substance consisting of molecules characterized by the sequence of one or more types of

monomer units and comprising a simple weight majority of molecules containing at least 3 monomer

units which are covalently bound to at least one other monomer unit or other reactant and which

consists of less than a simple weight majority of molecules of the same molecular weight.

These intermediate oligomers are not isolated and are used in total in STEP 2.

STEP 2:

To the molten (80'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 5O%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 for each mole

of 2-(chloromethyl)-oxirane (B) used in Step 1.

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

<I% OZ as measured by Draeger tubes to eliminate any potential fire/explosion hazard with the ensuing

Carbon Disulfide addition. The reactor is then sealed.

While the relative amount of primary amine to secondary amine from starting material to the

intermediate oligomeric amine changes in STEP L, the total number of primary amine and secondary

amine sites do not. (For every mole of primary amine alkylated a mole of secondary amine is formed).

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

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

dithiocarboxytation reaction on the nucleophillic amine sites. The resulting product is shown in the

reaction scheme below. (R=hexyl).
cs.! + l€oH

F*'nn'marlr t{*l

\*go'r*.."*,

Linear Character of Oligomers Described in Part 1:

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

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

chloromethyl)-oxirane with N1-(6-aminohexyl)-1,6-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)-L,6-hexanediamine were titrated with 0.L

N HCI to a pH of 3.8. This titration required 13.6 mls of titrant which yields 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 isreactive 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 /AVt=% tertiary amine content or

approximately 3.5o/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.