LIST OF REACTANTS

and PRODUCTS

FOR PROCESS

DESCRIPTION Material Designation Material Name A N

1-(6-a minohexyl)-L,6-hexa

ned ia mine B (2-cholo rmethyl)-oxi

ra ne 

## c intermediate oligameric

polya mine D aI

kylated N1-(6-a minohexyl)-1,6-hexa

nedia mine 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 minohexyl

)-1,6-hexa

ned iam ine) 

### K sodium

chloride

NONPOLYMERIC NATURE OFNCS 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 oneor more

types of monomer

units andcomprising

a simple 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

thisa polymer,

by EPA definition

it does not qualify

asa polymer. The pages

5 and5a in the PMN notice are therefore

filled out for completeness

to avoid anydelays

or questions,

but it is the opinion

of this author

that pages

4 and 4a should

hold precedence. STEP 1: Inthe first

stepmolten 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 asepichlorohyrin), 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) 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

residuesis not possible andensures

the formation

of the intermediate

oligomeric

product denoted

as INTERMEDIATE

PRODUCT

C asshown

in the reaction

scheme below. For

example

the simplest intermediate

oligomer

product, where n=1,

would bethe 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 andcomprising

a simple weight majority of molecules

containing

at least 3 monomer units which arecovalently

bound to at least

oneother 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

andare used

in total in STEP

2.

STEP 2: Tothe 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 yielda 5O%to

55% solution of the NewChemical

(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

formedby the ensuing addition of carbon

disulfide

(H) to the mixture

of polyamine oligomer

(C) and unreacted

(A), and in the finalproduct contain freesodium

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 isto 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 andsecondary 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 andsecondary

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 pHof 3.8. This

titrationrequired

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

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 pH of 3.8. This

yields an amine

value (AV2) for the solution

of 20.Thus the tertiary

amine contentcan be calculated as AV2 /AVt=% tertiaryamine content or approximately

3.5o/o. This data establishes

that the oligomer

forming the backbone

of the NC

is composed

almost entirely primary andsecondary

amines. Thatis, the oligomer

is almost

entirely linear in nature.