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Nylon 66 fundamentals and its processes

Nylon 66 fundamentals and its processes

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Published by 5161440
Nylon 66 fundamentals and its processes
Nylon 66 fundamentals and its processes

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Nylon
66
Fundamentals andIts
Processes
Ping
L.
Ku
10951
Stepney
Road,
Chester, Virginia
23831
(Former Associate
of
Allied Corp.)
ABSTRACT
The objective of this
paper
is
to search for andcritically examine the pertinent details of the currentbulk continuous nylon
66
processes (described n thepatents), which are practiced
or
followed by mostnylon producing industries. The
two
monomers formaking nylon
66
and their homologum includingdibasic and monobasic acids, diamines, andpriqamines show very interesting melting point behav-
ior.
On the other hand, compounds containing evennumbers of carbon atoms show consistently highermelting points than the neighboring
odd
numbercompounds of higher molecular weights. However,the boiling points of aUfour Series follow the usualrule: The higher the molecular weight, the higherthe boiling point.
It
has been proven tlrat the qualityof nylon
66
has
been greatly improved by loweringthe residence time during the polymerization.
For
instance, the spinning mte employed was
at
a levelof
7000
mlmin, and the tensile strength of the spunyarn was much improved, which was attributed
to
the overall quality of the polymer.
INTRODUCTION
paper centers on the polymerization aspect of the ny-lon
66
production processes. When one converts mon-omor to polymer, some of the important parameterswhich are to
be
controlled are justifiably discussed:molecular weights, molecular weight distributionThe polymerization reaction is generally recognizedas the primary
or
fundamental
step
in
the manufactureof high-polymer containing products; therefore, this
Advances in Polymer Technology,
Vol.
6,
No.
3,
267-275 (1986)
0
1986
by John Wiley
&
Sons, Inc.
CCC
0730-6679/86/030267-09$04.00
 
NYLON
66
(MWD), and degree of linearity, all of which do affectthe end-product properties.Furthermore, the orientation process (which isachieved by the spinning and drawing steps) is dis-cussed since such technology serves to significantlyimprove the fiber tensiJe strength.
NYLON
66
POLYMERIZATIONFUNDAMENTALSChemistry'-4
There are various methods in preparing a polymer;nylon
66
is synthesized via condensation polymeri-zation. The two monomers used for making nylon
66
are hexamethylenediamine (HMDA) and adipic acid(AA). Both are soluble in water, and both aqueoussolutions are miscible and stable at ambient conditionswith a solid content of about
47%.
Upon heating to180°C the carboxyl and amine groups will react toform one molecule, namely, hexamethylene diam-monium adipate, or a nylon salt:
H3i(
This salt is unstable at high temperatures since itwill split
off
a water molecule to become nylon
66
asfollows:
Y
r!
0 0
Subsequently, the condensation polymerization takesplace:
H H
I
I
n
H-[-N-(CHz)6-N~-(CHz)~-~H
--*
0
II
0
II
H
r
I
H-[-N~CHZ)~-N-C-(CHZ)~~-I"~H
II
0
Generally, the rate of the condensation polymerizationis relatively slow, and the reaction will continue untilall or one of the reactants is consumed. Since thecharged amount of reactants
are
stoichiometricallycontrolled, the degree of polymerization
is
able to
be
predicted. However, the theoretical approach does notalways conform with the actual field practice, and
so
an access amount of AA is charged.
As
the reaction continues, water released from re-action in the system is accumulating, which needs tobe removed by vacuum or slow venting. While wateris being removed, the viscosity or the system in-creases, thus slowing down the reaction. For a de-sired high molecular weight, the polymerization timemust be extended, causing a long residence timefor the polymers. This is a major disadvantage of theprocess. About nine years ago, DuPont in Canadamodified the patented process, whose residence timewas greatly reduced. Following the patents, the new-ly invented process will
be
discussed in at the endof this section.
Properties
of
the Monomer2
Adipic Acid
and
Its
Analogues.
The dibasic acidshaving two carboxyl groups at each end of the straightmethylene chains are all crystalline solids of highmelting point. Table
I
shows that, as the methylenegroup length increases, the melting point drops, in-dicating association attributable
to
the methylene group.It is quite interesting that the acids having an evennumber of carbon atoms invariably are higher meltingand less soluble than their neighboring high or lowhomologs having an odd number
of
carbon atoms.On the other hand, the homologous compoundshaving monocarboxyl group at only one end showmuch lower melting points as indicated in Table
11.
This means a dibasic monomer exhibits a much highermelting point as well as
T,
(Ref.
5,
p.
409).
The data
also
show the same characteristics that the meltingpoints of even number carbon atoms are higher thantheir neighboring compounds of high odd carbonnumbers.
Diamines, Primary Amines and Their Homo-loguess.
Hexamethylenediamine (HMDA), one of thetwa monomers for making nylon, may be readily pre-pared from adipic acid, which is the other monomerfor nylon
66,
using the adiponitrile process6
(3)
268
VOL.
6,
NO.
3
 
NYLON
66
A
homologous diamine series with methylene
pups
between the intermediates, (CH,), with n
=
0-6,
islisted in Table
III.
The boiling points increase withinmasing mlecular
size.
However,
the
melting
points
of the series do not follow the trend of molecularsizes but vary according to even or odd methylenegroups within the intermediates
of
diamines. Forinstance, the melting point for tetramethylenediamineis higher (27°C) than that (9°C) of pentamethylene-diamineOn the homologues
of
primary arnines, listed inTable
IV,
whose basic structure is similar to that ofamino acid (for nylon
6)
with the exception of theCH3 group at one end instead
of
a carboxylic group,exhibit the same phenomena
as
even number car-bon atoms. They have higher melting points thantheir neighboring compounds, including those withhigher molecular weights. Data on boiling points ofthis series show the same trend
as
shown in otherseries.
Structure
and
Properties
of
Nylon
66
and
610-Unstretche&
The Effect
of
the Length
of
Methylene Groups-On Melting Points
of
Nylons.
In Figure
1,
a com-parison of the two curves,
A
(nylon
66)
and
B
(nylon
610),
shows that nylon
610
has eight rnethylene groupshaving a low melting point. The nylon
66,
which hasonly four (CHI) in dibasic acids, results in a highermelting point.
The Effect
of
Odd
and
Even Methylene Groupson Melting Points.
It is observed from the two curvesin Figure 1 that the even number of CH, groups withinthe intermediates, diamines, show consistently highermelting points than their neighboring high
carbon
numbers for curve
A
(nylon
66).
CurveB,nylon
610,
shows the same trend, but its melting point isgenerally lower because of longer
(CH,)
group with-in the carboxylic intermediates. This agrees withdata in Tables I and
I1
in either series of odd or evenCH2 groups.
Properties
of
Nylon
M4*’
Table
V
shows some properties
of
nylon
66
at tex-tile and industrial levels. Their tensile strength values
are
slightly higher for the industrial grade, even thoughits melting point and T, are significantly low, com-pared to those of nylon
&not
listed here. This in-consistency makes the results inconclusive. Gener-ally, a high T, results in high tensile strength.
TABLE
I
Dibasic Acids’
AcidFormulaOxalicMalonicSuccinicGluta~icAdipicPimelicsubericAzelaicSebacicmp(”C)
187’135185
151
105142
I06
13497.5
Solubility
(g/1OOo
g
H20)
10.2”6.8”63.9”
1
.4152.514
0.
I4l6
.I
i38I6
,215
~~ ~
The
dihydrate
melts
with
loss
of
HP
t
100°C
TABLE
I1
Monocarboxyl or Saturated Fatty Acids
No.
of
Carbon mPAcid Atoms Formula (“C) bp (“C)FormicAceticRopionicButyricValericCaproicHeptylicCaprylicPelargoricCapricUndecy icLauric
I
2345
6
789
10
I1
128.4
loo.
16.6118.0
-
2.0141
.O
-
.7 163.0-34.5187.0
-
1.5205.0
-
11.0
223.516.5237.012.5254.031.3269.028.0
-
43.6
102
(1
mm)
TABLE
I11
Diamines’
Hydrazine
0
H2NNH2
2.0
113.0
Ethylenediamine
2
H~NCHZCH~NH~
8.5
117.0 0.892
Trimethylenediamine
3
H~NCH~CHZCH~NH~
135.5 0.844
TetramethlenePentamethyleneHexamethylenediamine
4
H2NCH2CH2CH2CH2NH2
27.0 158.0
diamine
5
H2N(CH”W
9.0 178.0 0.855
diamine
6
Hd’WU”2
39.0
I%.O
ADVANCES
IN
POLYMER TECHNOLOGY
269

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