Note: Descriptions are shown in the official language in which they were submitted.
a
... ~~~r~~~~r D. Z . 0050/43295
HIGH SPEED SPUN FILAMENT YARNS EASED ON POLYCAPROLACTAM
AND PRODUCTION THEREOF
The present invention relates to filament yarns
having a relative viscosity RV of from 2.0 to 3.0
(measured at a concentration of 1 g of yarn per 100 ml in
96$ strength by weight sulfuric acid) based on polycapro-
lactam, obtainable by
(a) extruding a melt consisting essentially of poly
caprolactam through a spinneret to form polycapro
lactam filaments,
(b) cooling the filaments thus produced, and
(c) taking off the cooled filaments at a speed of at
least (3600 + 1250 x (3.0 - RV)] m/min,
wherein the polycaprolactam used was prepared in the.
presence of at least one dicarboxylic acid selected from
the group consisting of
C,-Clo-alkanedicarboxylic acids,
- C5-C8-cycloalkanedicarboxylic acids,
- benzene- and naphthalene-dicarboxylic acids which
may carry up to two sulfonic acid groups and whose
carboxylic acid groups are not adjacent to each
other,
- N-Cl-C~-alkyl-N,N-di(C,-Clo-alkanecarboxylic acid)-
amine,
- 1,4-piperazinedi(C,,-Clo-alkanecarboxylic acid).
The present invention further relates to a
process ~~or producing these yarns, to the use thereof for
manufa$turing sheetlike structures, and to sheetlike
structures from these yarns.
In the high speed spinning of polyamides, the
filaments emerging from the spinneret are in general
taken off from the face of the spinneret at speeds of
above 3000 m/min, while in conventional spinning the
takeoff speeds a're in general not more than about
1200 m/min.
Compared with conventional spinning, high speed
a
2 _ O.Z. 0050/43295
spinning generally offers the advantage of higher pro-
ductivity. In some cases, especially in the case of
polycaprolactam, the operation of drawing can be dis-
pensed with in certain circumstances . A further advantage
of high speed spinning is that the spinning and winding
are in general less affected by the moisture content and
temperature of the ambient air than in conventional
spinning. Furthermore, the storability of the wound-up
yarns until required for further processing is in general
improved compared with conventionally spun yarns. More-
over, high speed spun filament yarns are in general
particularly useful for draw-texturing, draw-warping and
draw-sizing.
Draw-texturing comprises drawing and texturing
in one operation, the effect of texturing being to create.
a special fiber structure through direction-specific
orientation of the macromolecules. This generally results
in higher elasticity, bulk and thermal insulation com
pared with flat yarns. For improved further processing
such yarns can be subsequently oiled and/or intermingled.
The manufacture of warg-knitted or woven material
requires a multiplicity of yarns being fed side by side
in a parallel arrangement as a warp into the warp
knittin or weaving machine. For this purpose several
g
hundred to several thousand -yarns are wound together onto
a beam. In the course of being beamed the yarns are
frequently intermingled, reoiled, paraff inated or sized
to imprpve their compaction and further processing. A
plurality of such beams can be combined in a further
operation to increase the number of yarns. The production
' beam can be combined with a conjoint
of a. ( partial ) warp
drawing of the entir~ yarn sheet (draw-warping) or
similarly with sizing of the yarn sheet (draw-si.xing), in
which the yarns are coated with a nixing agent to improve
their running Properties and their mechanical integrity.
. Similarly, the drawing step can be carried out in
a conventional manner inanediately following spinning or
o.
r ..:
- 3 - O.Z. 0050/43295
in-line therewith.
EP-B-201 139 describes a melt spinning process
for producing polyamide filaments, characterized in that
a molten polymer mixture which contains a low molecular
weight additive such as water and has a relative viscos-
ity of from 2.0 to 3.0 (measured in 96$ by weight sul-
furic acid) is extruded, the filaments formed are cooled,
and the cold filaments are taken off at a speed of more
than 3200 m/min. Yarns from polycaprolactam prepared in
the presence of a dicarboxylic acid acting as chain
regulator are not described.
DE-A-4,019,780 describes a process for producing
polycaprolactam in the presence of dicarboxylic acid
' chain regulators. Yarns spun at the high takeoff speed
of 4250~m/min from the polycaprolactam described therein.
(relative viscosx.ty RV = 2.36) proved to be comparable to
prior art yarns in breaking strength and breaking exten-
sion.
A disadvantage of high speed spun yarns and of
drawn or draw-textured yarns obtained therefrom is that
in general they have lower tenacities at break than
conventionally spun yarns drawn or textured to the same
extension at break. Furthermore, the stress-strain
(force-elongation) curve of high speed spun yarns is in
general too flat.
Compared with high speed spun nylon-6,6 (poly
hexamethyleneadipamide), furthermore, high speed spun
polycapzclactam yarns have after draw-texturing to the
same extension at break the disadvantage of a lower crimp
stability.
' It is' an object of the present invention to make
available high speed spun filament yarns based on poly-
caprolactam that are free of the abovementioned dis-
advantages. More particularly, the yarns shall have a
steeper stress-strain curve, an improved tenacity at
break and - in the case of. textured yarns - an improved
crimp stability.
:~.',0. Z . 0050/4325
We have found that this object is achieved by the
_filament yarns defined at the beginning.
We have also found a process for producing these
yarns, a use thereof for manufacturing sheetlike struc
tares, and sheetlike structures from these yarns.
The invention proposes spinning a melt consisting
essentially of the above-defined polyeaprolactam and
taking off the cold filaments at a speed of at least
[3600 + 1250 x (3.0 - RV)] m/min, preferably of at least
[3800 + 1250 x (3.0 - RV)] m/min. Spinning speeds of
greater than [3600 + 1250 x (3.0 - RV)] mlmin axe found
to give an unexpected improvement in the tenacity. This
is evident from the fact that the higher the spinning
' speed above [3600 + 1250 x (3.0 - RV)] m/min for a given
RV, the greater the increase in the tenacity of the.
resulting spun yarns. Commercial polycaprolactam does not
to the best of our knowledge show this effect to any
significant extent, if at all (see comparative examples).
Again, from observations to date, the effect does not
occur below a spinning speed of [3600 + 1250 x
(3.0 - RV)] m/min for a given RV.
The upper limit for the spinning speed is in
general not higher than 8000 m/min and depends
essentially on the viscosity of the melt to be spun and
on the spinning apparatus used.
The relative viscosity RV of the polycaprolactam
to be spun is in general within the range from 2.0 to 3.0
(measured' at a concentration of 1 g of the polycapro-
lactam'per 100 ml of 96% strength by weight of sulfuric
acid at 25°C), preferably within the range from 2.3 to
2.9. A polycaprolactam having an RV greater than 3.0 is
in general too viscous for high speed spinning, while a
polycaprolactam having an RV less than 2.0 does not in
general give stable filaments.
According to the invention, the relative viscos-
ity RV of the spun filaments is within the range from 2.0
to 3.0 (measured at a concentration of 1 g of filament
0
- 5 - O.Z. 0050/43295
per 1Q0 ml in 96~ strength by weight of sulfuric acid at
_25°C),.preferably within the range from 2.3 to 2.9.
The polycaprolactams used according to the
invention are prepared in the presence of at least one
~ dicarboxylic acid chain regulator. polycaprolactams of
this type are known for example from US-A-3,386,976 and
DE-A-40 19 ?80. The polycaprolactams of the invention are
preferably prepared on the lines of the single-stage
process described in DE-A-40 19 780.
Using a dicarboxylic acid chain regulator it is
advantageous for the caprolactam to be polymerized at
from 230 to 300°C, preferably at from 240 to 290°C, in
the presence of water as initiator.
Suitable apparatus for carrying out the polymer
ization is known to the person skilled in the art and.
described for example in DE-B-2,448,100, DE-B-1,495,198
and EP-B-20,946.
The water used as initiator is in general used in
an amount of from 0.1 to 5$ by weight, in particular of
from 0.5 to 3$ by weight, based on caprolactam.
The dicarboxylic acid used is preferably of the
type which acts as a difunctional chain regulator in the
hydrolytic polymerization of caprolactaan and does not
decompose under the conditions of the polymerization and
of spinning or lead to discolorations or other undesir-
able phenomena. Furthermore, the dicarboxylic acid used
must not for example have a chain limiting effect due to
the formation of a ring structure. Examples of dicar-
boxylic acids that are unsuitable are succinic acid and
phthalic acid, since they may have a chain limiting
effect due to ring closure.
Examples of suitable dicarboxylic acids are
Cd-Clo-alkanedicarboxylic acids such as adipic acid,
pimelic acid, suberic acid, azelaic acid, sebacic acid,
undecanedioic acid and dodecanedioic acid, preferably
adipic acid,
C~-C8-cycloalkanedicarboxylic acids such as
- 6 - O.Z. 0050/43295
cyclogentane-1,3-dicarboxylic acid and cyclohexane-
1,4-dicarboxylic acid, preferably cyclohexane-
1,4-dicarboxylic acid,
~
may
benzene- and naphthalene-dicarboxylic acids which
carry up to two sulfonic acid groups, or alkali metal
salts thereof, and whose carboxylic acid groups are not
adjacent to each other, such as terephthalic acid,
isophthalic acid, naphthalene-2,6-dicarboxylic acid and
5-sulfur-isophthalic acid, preferably terephthalic acid,
isophthalic acid and 5-sulfur-isoghthalic acid, and
mixtures thereof,
N-C1-C6-alkyl-N, N-di ( Cd-Clo-alkanecarboxylic acid) amine
such as N-methyl-N,N-di(caproic acid)amine and N-methyl-
N, N-dl. ( aCetlC .acid) dnllne,
1,4-piperazinedi(C,,-C6-alkanecarboxylic acid) such as.
1,4-piperazinediacetic acid, 1,4-piperazinedipropionic
acid, 1,4-piperazinedibutanoic acid, 1,4-piperazinedi-
pentanoic acid, and 1,4-piperazinedihexanoic acid,
preferably 1, 4-pip~erazined3.acetic acid, 1, 4-piperazinedi-
propionic acid.
Filaments containing dicarboxylic acids with
tertiary amino groups are in general readily dyeable with
anionic dyes. In some cases this can be desirable if
particularly deep colors; are to be achieved.
Filaments that contain sulfonate groups are in
general readily dyeable with cationic dyes but less
receptive to anionic dyes, which occur for example in
many foods and beverages, which in general results in
reduced staining.
~ ~ The dicarboxylic acid is in general added at the
' top of the polymerization zone, from where it is
thoroughly mixed in with the melt to be polymerized.
However, the dicarboxylic acid can also be added before
or during the polymerization.
The amount of dicarboxylic acid used is in
general from 0.05 to. 0.6, in particular from 0.1 to 0.5,
mol%, based on caprolactam.
~1.~'~3~5
- 7 - O.Z. 0050/43295
In a further embodiment, designed to improve the
anionic dyeability, the dicarboxylic acid chain regulator
is combined with a diamine chain regulator of the type
N, N=di ( C1-C6-alkyl ) amino ( CZ-Clz-alkyl ) amine .
Examples are 2-diethylamino-1-ethylamine,
6-dimethylamino-1-hexylamine, 3-dimethylamino-1-propyl-
amine, 3-diethylamino-1-propylamine, preferably
3-dimethylamino-1-propylamine, 3-diethylamino-1-propyl-
amine.
Preference is given to using the diamines of type
N, N-di ( C1-C6-alkyl ) amino ( CZ-C,Z-alkyl ) amine in amounts of
from 0.05 to 0.3, in particular preferably from 0.1 to
0.3, mol%, based on caprolactam. The use of less than
- 0.05 mol% does not in general lead to any significant
improvement in dyeability, while if the amount is above
0.3 mol% the chain limiting effect of these amines will
in general become excessive.
In another embodiment, primary monoamines can be
used alongside the dicarboxylic acid chain regulators
mentioned, if a reduction in the carboxyl group content
and an improvement in the melt stability of the product
are desired.
Suitable primary monoamines are Cd-C,2-alkylamines
and C6-aryl-C1-C,-alkylamines such as butyl-, pentyl-,
hexyl-, heptyl-, octyl-, nonyl-, decyl-, undecyl- and
dodecyl-amine and phenylmethyl-, phenylethyl-,
phenylpropyl- and phenylbutyl-amine, preferably
hexylamin~,-octylamine, decylamine and phenylethylamine.
The primary monoamines are preferably used within
the range from 0.05 to 0.5 mot%, particularly preferably
' from 0.l to 0.4 mol%, based on caprolactam.
The polymerization can in general be carried out
at a pressure within the range from 100 to 2000 kPa. A
particularly preferred embodiment comprises carrying out
the polymerization continuously under a uniform pressure
of from 100 to 190, preferably of from 100 to 170, kPa,
measured in the vapor phase above the polymerization
~ .-~. r...~ r~ P'
A . :ofr~.2..~ S'~ ~'~
- 8 - ~.Z. 0050/43295
zone, while maintaining a water content of from 0.1 to
0.5, in particular from 0.1 to 0.4, % by weight in the
melt. It will be understood that the excess water intro-
duced at the top into the reaction zone is continuously
distilled off as a function of the pressure employed in
order to maintain the aforementioned water content.
The polymerization time is in general from 5 to
20, preferably 8 to 12, hours and depends essentially on
the properties desired for the product.
The polycaprolactam is advantageously removed
from the polymerization zone at the lower end thereof.
The level of chemically bound dicarboxylic acid
(determinable by hydrolysis of the polycaprolactam and
subsequent analysis) in the extracted and dried end
product is in general within the range from 5 to.
60 mmol/kg, preferably within the range from 10 to
50 mmol/kg. Values below 5 mmol/kg do not in general
bring the desired improvement in the properties of the.
high speed spun yarns. Values above 60 mmol/kg do not in
general make it .possible to obtain the relative
viscosity/molecular weight desired for preparing the
polymer.
If the end product additionally contains chemic-
ally bound diamines, the level thereof is in general
within the range from 5 to 30 ma~aollkg, preferably from 10
to 30 manol/kg, in which case the level of chemically
bound dicarboxylic acids will in general be within the
range f~,om 10 to 50, preferably from 15 to 50, nunol/kg.
-~ The level of water-extractable residual monomers
and oligomers in the ready-to-spin polycaprolactam is
' chosen to be within the range from 0 to 2, preferably
from 0 to l, % by weight of the polycaprolactam.
The water content of the ready-to-spin poly
caprolactam is in general within the range below 0.4,
preferably from 0.02 to 0.15, % by weight.
The unintermingled filament yarns of the inven-
tion generally have an extension at break within the
_ g _ O.Z. 0050/43295
range~from 30 to 100, preferably from 40 to 90$. By
intermingling it is possible if desired to reduce the
extension at break still further.
The polycaprolactam to be spun and the filaments
obtained therefrom may contain customary additives and
processing aids. The proportion thereof is in general up
to 5, preferably up to 3, ~ by weight, based on the total
weight of the polycaprolactam.
Customary additives are for example antioxidants,
thermal stabilizers, W absorbers, dyes, pigments,
delusterants and antistats.
Antioxidants and thermal stabilizers are for
example sterically hindered phenols, hydroc~uinones,
- phosphites and derivatives and substituted
representatives of this group and mixtures thereof, and.
also copper compounds such as copper(I) iodide and
copper(II) acetate.
Examples of W stabilizers are substituted
resorcinols, salicylates, benzotriazoles and benzo
phenones, which in general are usable in amounts of up to
1% by weighty here it is also possible to use
manganese(TI).
Suitable colorants are organic dyes and the
customary spin-dyeing agents such as chromium or copper
complexes, inorganic pigments such as titanium dioxide
and cadmium sulfide, iron oxides or pigment grade carbon
black.
~ antistats it is possible to use the customary
substas'fces, for example polyalkylene oxides and deriva
tines thereof.
' The addition of the additives can take place at
any stage of the manufacture of the filament yarns of the
invention, but it is advantageous to add the stabilizers
early in order to achieve stabilization sight from the
beginning. Accordingly, the stabilizers are in general
added even during the polymerization process, provided
they do not interfere therewith.
- 10 - O.Z. 0050/43295
The filament yarns of the invention can if
desired be drawn, draw-twisted, draw-wound, draw-warped,
draw-sized and draw-textured in a conventional manner.
The drawing to a flat yarn can be carried out in one
operation with the high speed spinning process, producing
fully drawn yarn, FDY, or fully oriented yarn, FOY, or in
a separate operation. Draw-warping, draw-sizing and draw-
texturing are in general carried out separately from the
high speed spinning process.
The filaments of the invention can be processed
into fibers in a conventional manner. Sheetlike struc-
tures can be manufactured for example by weaving or
knitting.
The high speed spun yarns of the invention are
advantageous over the prior art,yarns in possessing an.
improved tenacity, a steeper stress-strain curve and an
improved crimp stability. Furthermore, from experience to
date, yarns of the invention have fewer drawing defects
than the prior art high speed spun polycaprolactam yarns .
Further studies have shown that the polycapro-
lactam used according to the invention has a reduced melt
elasticity and develops a special crystal morphology on
fiber formation. The improved properties of the yarns
according to the invention may be presumed to be con-
nected with the special elasticity of the polymer melt
and the special morphology of the filaments.
EXAMPLES
~The polycaprolactam was produced using a precon-
densat~on tube having a mechanically agitated first
reaction zone as described in EP-A-20,946. The precon-
densation tube had a capacity of 340 1 and was heated
with a heat transfer fluid.
The relative viscosity RV of~the polycaprolactam
and of the spun filaments was determined at a concentra
tion of 1 g per 100 ml in 96% strength by weight sulfuric
acid at 25°C.
The residual moisture content was determined by
~~,.~"~3'~~
- 11 - O.Z. 0050/43295
the vapor pressure method using an Ackermann instrument.
The levels of chemically bound dicarboxylic acid
and of chemically bound diamine are known from the
starting quantities. The levels can also be determined by
hydrolyzing the polycaprolactam in dilute mineral acid
and then analyzing the mixture thus obtained.
To characterize the melt elasticity of the
polycaprolactam, the elastic compliance Je, determined
under oscillatory shearing, of the samples regulated
according to the invention with dicarboxylic acid was
referred to the compliance J~,r~t of standard products of
the wane viscosity regulated with propionic acid.
_ The measurements were carried out on an RUS2
Rheometrics dynamic spectrometer using a plate-plate
arrangement radius 25 mm, distance ~. mm) at 250~C and a.
shear amplitude of 0.3. The quantities measured were the
storage modules G' and the loss modules G" for circular
frequencies of from 0.3 rad/sec to 100 rad/sec. The
measured curve was marked at that circular frequency at
~20 which the loss modules had just reached the value
G"=103 Pa. From the corresponding storage modules G' the
compliance is given by equation 1 as
Je ~ G./~G,.)2 a G~/106 Pa2 ~eq~ 1)
The reference compliance J~,s~t f or the propionic
acid regulated product of the same viscosity was deter-
mined in~the same way. Finally, the two compliances were
expressed as a ratio R (equation 2)
a _ _
R = J"/Js,rsi (eq. 2)
to derive a rheological parameter for the melt elasticity
that permits detection of differences in the elasticity
of the melt with a very high resolution.
The breaking extension was determined using an
Llster Tensorapid I instrument in which the clamped length
- 12 - O.Z. 0050/43295
was 2Q0 mm in the case of partially, oriented yarn (POY)
and 500 mm in the case of drawn and textured yarns. The
time to break the yarns was of the order 20 t 2 seconds.
The pretensioning force was 0.025 cN/dtex in the case of
POY, 0.05 cN/dtex in the case of drawn yarn and
0.2 cN/dtex in the case of textured yarn.
The breaking tenacity R$ was determined according
to equation 3
R$ = F$/Tt" ( eq. 3 )
-where Fx is the ultimate tensile strength [cN] and Tt" the
original linear density [dtex]. The value employed for
the ultimate tensile strength was the highest value
recorded in the breaking extension measurements.
The breaking extension E$ was expressed as the
ratio of the elongation oL at break to the original
length 1" of the specimen, according to equation 4:
E$ = of x 100%/1,, (eq.4)
where of is the difference between the length of the
specimen at break, 1g, and the original length 1".
These determinations were also recorded in graph
form as stress-strain or force-elongation diagrams.
The warping defects were determined at a warping
speed of 600 m/min using a hindley Standard Yarn
InspectQr.~series 1900.
'~ The crimp contraction, the crimp modulus and the
crimp stability of the textured yarns were all determined
in accordance with DIN 53 840.
In a few selected cases the morphology of the
spun filaments was characterized by X-ray small angle
scattering (XSAS). The XSAS measurements were carried out
in a pre-evacuated Kiessig chamber. The apertures in the
collimator tube were 0.4 and 0.3 aun in diameter, and the
distance A between the fiber specimen and the flat ~L-ray
- 13 - O.Z. 0050/43295
film ,(AGFA-GEAAERT, Osray M3) was 400 mm. The X-ray
source used was a Cu tube, operated at 37 kv and 36 mA,
whose R« line (wavelength a =0.15418 nm) was selected
for the measurements by means of a graphite primary mono-
chromator. By way of sample preparation for XSAS analysi-
s, th.e partially oriented yarn was wound on a frame with
the individual filaments inexactly parallel arrangement.
The fiber bundles from 0.7 to 1 mm in thickness were
subjected to a perpendicular X-ray beam with the fiber
axis in a vertical position. The exposure time was 20 or
40 h.
The meridian reflections of the XSAS films due to
the crystalline-amorphous superlattice of the POY fila-
ments was evaluated with the aid of a photometer (micro-
densitometer 3CS from Joyce Loebl). More specifically,.
the meridian reflections were scanned along the parallel
to the film equator running through the meridian maximum
using a gray wedge of optical density D = 0.95. The full
width at half maximum (FWF~i) of the resulting photometer
curve is a measure. of the thickness Ag of the crystal
Fibrils perpendicular to the fiber axis. The lateral
crystal thickness ng can be approximated as follows:
A~ = L ( nm) /B ( rad) ( eq. 5 )
where a is the X-ray wavelength and Brad) is the half-
value width of the photometer curve measured in radian.
B ( rad ) ~~s obtained f ram the FWHM value F3 ( ~ ) by the
equatibn:
.. _ _
Brad) - 8(mm)/A x F (eq~ 6)
where A is the distance between fiber sample and X-ray
film and F is the translation factor of the photometer.
Inserting A = 400 mm and F.= 5, equation 5 becomes
nF ~ (J~ ( nm) / H (mm) J ~ 2 ~ 10 3 ( eq . 7 )
a
~~..~;" i °~'~
- 14 - O.Z. 0050/43295
The polycaprolactam was spun by melting in an
extruder (Barmag 3E-24S, screw 38 mm in diameter, L/D=24)
and forced through a spinning jet (hole count 12, hole
diameter 0.20 mm, capillary length 0.40 mm). The result-
s ing filament yarns were first passed through a quench
cell (height 1600 mm, 0.4 m/sec transverse flow of air at
22°C and 65% relative humidity) and then through a free-
fall cell (height 2000 mm), taken off on an EMS-Invents
pilot spinning position via two pairs of godet rolls
150 mm in diameter, and wound up on an SW 46 1S-900
winder from Barmag.
The distance between jet and oiler was 1300 uua.
Drawing was carried out cold at 740 m/min on a
drawtwister (J5/10a, Rieter).
Draw-texturing was carried out at 600 or
800 m/min on an FKS6L-10 draw-texturing machine from
Barmag.
A. Preparation of golycaprolactam.
EXAMPLE 1
Molten caprolactam containing 0.5% by weight of
water and 0.53% by weight of terephthalic acid as chain
regulator was continuously fed with stirring under
atmospheric pressure into the first reaction zone of the
precondensation tube. The throughput was 25 kg/h. At the
same time a mixture of 70% by weight of polycaprolactam
(RA ~ 1.9) and 30% by weight of titanium dioxide (anatase
form) was~a.ntroduced into the first polymerization zone
at a 'rate of 225 g/h. The temperature of the first
reaction zone was 252°C. The heat of polymerization
evolved in the subsequent reaction zones was removed
through appropriate cooling with internal heat
exchangers . The temperature of the last reaction zone was
265°C.
After extraction with boiling water and sub-
sequent drying, the product had a relative viscosity of
2.39, a (chemically bound) terephthalic acid content of
.
- 15 - ~.Z. 0050/43295
36 mmol/kg, a residual moisture content .of from 0 . 046% by
weight and a titanium dioxide content of 0.3% by weight.
~The elastic compliance Je was 8.3 x 10°6 Pa-1 and the
relative index R was 0.78.
EXAMPLE 2
Caprolactam was polymerized by the method of
Example 1 using 0.80% by weight of terephthalic acid as
chain regulator. The throughput was 30 kg/h and the rate
of addition of the titanium dioxide mixture was 270 g/h.
The other experimental conditions of Example 1 were
retained.
The product had a relative viscosity of 2.32 and
a (chemically bound) terephthalic acid content of
54 mmol/kg, The elastic compliance J~ was 5.1 x 10°6 Pa-1
and R was 0.48.~The titanium dioxide content was 0.3% by
weight and the residual moisture content was 0.016% by
weight.
EXAMPLE 3
Caprolactam having a water content of 0.7% by
weight was polymerized by the method of Example 1 under
a gauge pressure of 30 kPa using 0.21% by weight of
terephthalic acid as chain regulator. The throughput was
34 kg/h: The temperature of the first reaction zone was
set to 240°C. No titanium dioxide was added.
The product had a relative viscosity of 2.71 and
a (chemically bound) terephthalic acid content of
14 mmol/kg. The residual moisture content was 0.019% by
w~ight.
EXAMPLE 4
3p ~ ~ Caprolactam having a water content of 0.6% by
weight was polymerised by the method of Example 3 using
0.29% by weight of terephthalic acid as chain regulator.
The temperature of the first reaction zone was set to
245°C. The other experimental conditions of Example 3
were retained. No titanium dioxide was added.
The product had a relativ~ viscosity of 2.71 and
a (chemically bound) terephthalic acid content of
~~.3'~3'~~
- 16 ° p.Z. 0050/43295
19 mmol/kg. The residual moisture content was 0.021 by
weight .
EXAMPLE 5a
Caprolactam having a water content of 0.6% by
weight was polymerized by the method of Example 3 using
0.37$ by weight of terephthalic acid as chain regulator.
The temperature of the first reaction zone was set to
251C. The other experimental conditions of Example 3
were retained. No titanium dioxide was added.
The product had a relative viscosity of 2.6? and
a (chemically bound) terephthalic acid content of
25 mmol/kg. The residual moisture content was 0.091% by
weight.
EXAMPLE 5b
Caprolactam containing 0.5% by weight of water
and 0.26% by weight of adipic acid as a chain regulator
was polymerized by , the method of Example 3. The
throughput was 35 kg/h. The temperature of the first
reaction zone was set to 250C. No titanium dioxide .was
added. ,
The product had a relative viscosity of 2.6'7 and
a (chemically bound) adipic acid content of 20 mmol/kg.
The residual moisture content was 0.018% by weight.
EXAMPLE 5c
Caprolactam was polymerized in the presence of
0.5% by weight of water, 0.81% by weight of the lithium
salt of 5-sulfoisophthalic acid as a chain regulator and
0.18% by-laeight of titanium dioxide. After extraction
with boiling water and subsequent drying the product had
a relat~.ve viscosity of 2.55, a titanium dioxide content
of 0.20% by weight and a residual moisture content of
0.031% by weight.
B. sigh speed spinning of polycaprolactam
EXAMPLE 6
The polycaprolactam prepared in Example 1 was
spun from the melt at 265°C at (a) 4500 m/min and (b)
5500 m/min. The RV of the yarn was 2.48. The as-spun
- 17 ~ O.Z. 0050/43295
linear density was in case (a) dtex 50 f 12 and in case
(b) dtex-41 f 12. After drawing the yarns spun at
4500 m/min had a linear density of dtex 44 f 12.
Table 1 shows the results.
COMPARATIVE EXAMPLE 1
The run of Example 6 was repeated with a commer-
cial polycaprolactam (chain regulator: propionic acid,
content in product - 40 mmol/kg, RV = 2.37, titanium
dioxide - 0.3~ by weight, elastic compliance
11.5 x 10'6 Pa'1, residual moisture content 0.044 by
weight) under otherwise identical conditions.
Table 1 shows the results.
EXAMPLE 7
The polycaprolactam prepared in Example 2 was
spun from the melt at 265°C at (a) 5500 m/min and (b)
6000 m/min. The RV of the yarn was 2.31. The as-spun
linear density was ( a ). dtex 42 f 12 and ( b ) dtex 43 f 12 .
Table 2 shows the results.
COMPARATIVE EXAMPLE 2
The run of Example 7 was repeated with the same
commercial polycaprolactam of Comparative Example 1 under
otherwise identical conditions.
Table 2 shows the results.
EXAMPhE 8
The polycaprolactam prepared in Example 3 was
spun from the melt at 275°C at (a) 4500 m/min, (b)
5500 m/min and (c) 6000 m/min. The RV of the yarn was
2.79. The:as-spun linear density was (a) dtex 54 f 12,
(b~ dte~'S1 f 12 and (c) dtex 52 f 12. The as-drawn
lineal -density was dtex 45 f 12 in the case of the
spinning speed of 4500 m/min.
Table 3 shows the results.
..,v.:.w::-::~.,.,,. r..v:... .. . ~, ~ .
- 18 - O.Z. 0050/43295
COMPARATIVE EXAMPLE 3
The run of Example 8 was repeated with a commer-
vial polycaprolactam (chain regulators propionic acid,
content in product - 20 mmol/kg, RV = 2.68, elastic
compliance 10.0 x 10-6 Pal, residual moisture content
0.012% by weight) under otherwise identical conditions.
Table 3 shows the results.
EXAMPLE 9
The polycaprolactam prepared in Example 4 was
spun from the melt at 275°C at 4500 m/min. The RV of the
yarn was 2.83. The as-spun linear density was
dtex S 4 f 12 . The yarn was then draw-textured at ~i 0 Om/min
on a draw-texturing machine ( Barmag FK 6L-10 ) at <3 heater
temperature of 180°C with a D:Y ratio of 2.33 to HE yarn
(disk combination and arrangement: Ceratex all-ceramic.
disks arranged 1:5:1).
Table 4 shows the results.
CO1KPARATIVE EXAMPLE 4
The run of Example 9 was repeated with, the
commercial polycaprolactam of Comparative Example 3
(residual moisture content 0.017% by weight) under
otherwise identical conditions.
Table 4 shows the results.
EXAMPLE 10
The polycaprolactam prepared in Example 5a was
spun from the melt at 275°C at 5500 m/min. The RV of the
yarn was 2.69. The as-spun linear density was
dtex 5 4 :~. ~ 12 .
w Table 5 shows the results.
~ COMPARATIVE E~~AMPLE 5
The run of Example 10 was repeated with a comnner-
cial polycaprolactam (chain regulator: propionic acid,
content in product - 20 ~nol/kg, RV = 2.66, elastic
compliance 10.0 x 10°6 Pa'1, residual moisture content
0.098% by weight) under otherwise identical conditions.
Table 5 shows the results.
,-
- 19 - 0>Z. 0050/43295
EXAMPLE 11
'- A polycaprolactam prepared analogously to Example
5a (0.37$ by weight of terephthalic acid as chain regu-
lator, relative viscosity 2.67, chemically bound tere-
phthalic acid content of end product 25 mmol/kg, residual
moisture content 0.02 by weight) was spun from the melt
at 275°C at 4500 mlmin. The RV of the yarn was 2.78. The
as-spun linear density was dtex 54 f 12. The yarn was
then draw-textured at 800 m/min on a draw-texturing
machine ( from Barmag, FR6L-10 ) using a heater temperature
of 180°C, a Ceratex disk combination 1:5:1 and a D:Y
ratio of 2.2.
Table 6 shows the results.
_ COMPARATIVE EXAMPLE 6
The run of Example 11 was repeated with a com-.
mercial polycaprolactam (chain regulator: propionic acid,
content in product - 20 mmol/kg, RV ~ 2.68, residual
moisture content 0.017% by weight) under otherwise
identical conditions.
Table 6 shows the results.
CO1~ARATIVE EXAMPLE 7 (analogously to DE-A-40 19 780)
Polycaprolactam prepared analogously to Example 4
of DE-A-40 19 780 with a relative viscosity of 2.36, a
titanium dioxide content of 0.03% by weight and a
residual moisture content of 0.04% by weight was melted
at 269°C in an extruder (Barmag 3E, 3-zone screw 30 mm in
diameter with LTM ( low temperature mixing) , L/D = 24 ) and
forced i~hrough a jet (13 holes, hole diameter 0.20 mm,
capilla3ry length 0.40 mm) . The filaments were then cooled
down in a quench cell ( length 1500 mm, transverse quench)
with air at 24°C and 40% relative humidity and then
passed through a free-fall cell of 2200 nun in length to
windup.
Windup took place without godets using a winding
head ~rom Barmag (SW46 SSD) at 4250 m/min. The as-spun
linear density was dtex 56 f 13.
The distance between jet and oiler was 1300 aim.
~..3'~~"75
- 20 - O.Z. 0050/43295
Drawing was carried out cold on a drawtwister
(Rieter;_ J5/10a) at 605 m/min to an as-drawn linear
density of dtex 44 f 13.
- Table 7 shows the results.
COMPARATIVE EXAMPLE 8
The run of Comparative Example 7 was repeated
with commercial polycaprolactam (chain regulator: pro-
pionic acid, content in product = 40 mmol/kg, RV = 2.36,
titanium dioxide: 0.03%, residual moisture content: 0.04%
by weight) under otherwise identical conditions.
EXAMPLE 12
The polycaprolactam prepared in Example 5b was
spun from a melt at 275°C at (a) 4500 m/min, (b)
5500 m/min and (c) 6'000 m/min. The RV of the yarn was
2.78. The as-spun linear density was dtex 53 f 12 in case
(a), dtex 53 f 12 in case (b) and dtex 54 f 12 in case
(c). After drawing the yarns obtained at a spinning speed
of 4500 m/min had a linear density of dtex 44 f 12.
Table 8 shows the results.
EXAMPLE 13
The polycaprolactam prepared in Example 5c was
spun from a melt at 275°C at (a) 4500 m/min, (b)
5500 m/min and (c) 6000 m/min. The RV of the yarn was
2.57. The as-spun linear density was dtex 54 f 12 in case
( a ) , dtex 54 f 12 in case ( b ) and dtex 55 f 12 in case
(c). After drawing the yarns obtained at a spinning speed
of 4500 m/min had a linear density of dtex 44 f 12.
Table 8 shows the results.
COMPARATIVE EXAMPLE 9
' - -The runs of Examples 12 and 13 were repeated with
' a commercial polycaprolactam (chain regulator: propionic
acid, content in product ~ 20 mmol/kg, RV a 2.72,
residual moisture content: 0.033% by weight) under
otherwise identical conditions.
Table 8 shows the results.
'.
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