U.S. patent number 3,756,441 [Application Number 05/280,202] was granted by the patent office on 1973-09-04 for flash spinning process.
This patent grant is currently assigned to E. I. du Pont de Nemours and Company. Invention is credited to Ronald D. Anderson, Rudolph Woodell.
United States Patent |
3,756,441 |
Anderson , et al. |
September 4, 1973 |
**Please see images for:
( Certificate of Correction ) ** |
FLASH SPINNING PROCESS
Abstract
Process for preparing high quality plexifilaments from isotactic
polypropylene by flash extruding trichlorofluoromethane solutions
at temperatures from 200.degree. to 240.degree.C. and pressures in
excess of 900 psig, provided further that (MFR/c) .gtoreq.
1.13-0.04 (T-220) where Mfr is the melt flow rate of the isotactic
polypropylene at the instant of extrusion, with 2 .ltoreq. MFR
.ltoreq. 30, c is the concentration of the isotactic polypropylene
in the solution, expressed in weight percent, and T is the
temperature of the solution in .degree.C.
Inventors: |
Anderson; Ronald D. (Stuarts
Draft, VA), Woodell; Rudolph (Richmond, VA) |
Assignee: |
E. I. du Pont de Nemours and
Company (Wilmington, DE)
|
Family
ID: |
23072103 |
Appl.
No.: |
05/280,202 |
Filed: |
August 14, 1972 |
Current U.S.
Class: |
264/205; 264/53;
264/211.12 |
Current CPC
Class: |
E04C
3/12 (20130101); D01F 6/30 (20130101); D01D
5/11 (20130101); E04B 1/2604 (20130101); D01F
6/04 (20130101) |
Current International
Class: |
D01D
5/00 (20060101); E04B 1/26 (20060101); D01D
5/11 (20060101); D01F 6/04 (20060101); E04C
3/12 (20060101); D01f 007/00 () |
Field of
Search: |
;264/204-206,53,176F |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Woo; Jay H.
Claims
The embodiments of the invention in which an exclusive property or
privilege is claimed are defined as follows:
1. A process for the flash spinning of high quality
plexifilamentary material which comprises in sequence:
1. mixing sufficient isotactic polypropylene with
trichlorofluoromethane to obtain a solution wherein the
concentration of polypropylene is between about 2 and 20 percent by
weight,
2. adjusting the temperature and pressure of the solution until the
temperature is between about 200.degree.C. and 240.degree.C., the
pressure on the solution is in excess of 900 psig; and the melt
flow rate (MFR) of the isotactic polypropylene fulfills the
following formula:
(MFR/c) .gtoreq. 1.13 - 0.04 (T-220)
in which c is the concentration of the isotactic polypropylene in
the solution, expressed in weight percent and T is the temperature
(.degree.C.) of the solution, and wherein MFR is equal to a numeral
between 2 and 30, inclusive; and
3. extruding said solution abruptly into a region of lower
temperature and pressure so as to produce said plexifilamentary
material.
2. The process of claim 1 wherein the minimum MFR/c value is 15
percent greater than the value 1.13 - 0.04 (T-220).
3. The process of claim 1 wherein the temperature of the solution
in step (2) is between about 220.degree. and 235.degree.C.
4. The process of claim 2 wherein the temperature of the solution
in step (2) is between about 220.degree. and 235.degree.C.
5. The process of claim 1 wherein the pressure on the solution in
step (2) is high enough to maintain the solution as a single
phase.
6. The process of claim 5 wherein, after step (2) and before step
(3), the solution is passed through a pressure letdown chamber
where the pressure on the solution is lowered to a point at which
the solution forms a two-phase liquid, said solution remaining in
said letdown chamber not more than 30 seconds.
7. The process of claim 6 wherein the minimum MFR/c value is 15
percent greater than the value 1.13 - 0.04 (T-220).
8. The process of claim 6 wherein the temperature of the solution
in step (2) is between about 220.degree. and 235.degree.C.
9. The process of claim 7 wherein the temperature of the solution
in step (2) is between about 220.degree. and 235.degree.C.
10. The process of claim 1 wherein the polypropylene has a MFR
lower than that required to fit the equation in claim 1 and is
thermally degraded in the solution to a value that does fit said
equation.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a process for preparing a high quality
plexifilamentary product from isotactic polypropylene. More
particularly, the invention is concerned with the flash-extrusion
of solutions of isotactic polypropylene in trichlorofluoromethane
under certain specified conditions.
2. Description of the Prior Art
In U.S. Pat. No. 3,081,519 a method is described for preparing a
fibrillated web or plexifilament by flash extrusion (flash
spinning). In this process a polymeric solution at a temperature
above the boiling point of the solvent and at a pressure at least
equal to the autogenous pressure is extruded abruptly into a region
of lower temperature and substantially lower pressure. In a
selected concentration range and when the temperature of the
solution exceeds the "self-nucleation temperature" of the solvent
(approximately 45.degree.C. below the solvent critical temperature,
T.sub.c), flash vaporization of the solvent generates
extraordinarily large numbers of bubbles throughout the extrudate,
breaks through the confining bubble walls, and instantaneously
cools the extrudate, causing solid polymer to precipitate in highly
subdivided skeletal form. The resulting multifibrous yarn-like
strand has an internal fine structure of morphology characterized
as a three-dimensional integral plexus consisting of a multitude of
essentially longitudinally extended, interconnecting,
random-length, fibrous elements referred to as film-fibrils. These
film-fibrils have the form of thin ribbons of a thickness less than
four microns which intermittently unite and separate at irregular
intervals called "tie points" in various places throughout the
width, length, and thickness of the strand to form the integral
three-dimensional plexus. The fibrous strand comprising a
three-dimensional network of film-fibril elements is referred to as
a plexifilament and has utilities similar to those of spun staple
textile yarns. Alternatively, these interconnected fibrous networks
may be spread laterally, as by extruding through slot-shaped
post-orifice shrouds or by impinging the nascent strand on a solid
deflecting surface, to form continuous plexifilamentary webs which
may be deposited on a belt to form highly desirable nonwoven sheet
structures.
Certain plexifilamentary structures are desirably prepared from
isotacttc polypropylene, a relatively inexpensive polymer which
provides improved creep resistance, higher resilience, and higher
melting point as compared to plexifilaments of, e.g., linear
polyethylene. However, in attempting to prepare continuous
plexifilaments of polypropylene employing the above flash spinning
technique, difficulties have been experienced in consistently
obtaining strong, continuous strands with a high degree of
fibrillation throughout their length. One operable flash spinning
system has been discovered comprising isotactic polypropylene/1, 1,
2-trichloro-1, 2, 2-trifluoroethane solutions under prescribed
conditions of temperature, pressure and concentration as described
in U.S. Pat. No. 3,467,744. However, it has been an objective for
some time to discover conditions for preparing high quality
polypropylene plexifilaments from trichlorofluoromethane solutions,
since the latter solvent is not only more economical, but is also
eminently suitable as a flash extrusion solvent for linear
polyethylene, and use of a common solvent would greatly simplify
production of plexifilamentary products from either polyolefin at
will, employing a common facility. Although experiments have
domonstrated that good polypropylene plexifilaments can still be
obtained when a minor proportion of the operable 1, 1,
2-trichloro-1, 2, 2-trifluoroethane solvent is replaced by a
quantity of trichlorofluoromethane, this route is not attractive
since it leads to the need for dual solvent supply systems,
requires careful control of two-solvent feed ratios, and
complicates the requirements for a solvent recovery system.
SUMMARY OF THE INVENTION
A process for the flash spinning of high quality plexifilamentary
products of isotactic polypropylene has now been discovered which
comprises:
1. preparing a solution of isotactic polypropylene and
trichlorofluoromethane wherein the concentration of polypropylene
is between about 2 and 20 percent by weight, the temperature of the
solution is between about 200.degree.C. and 240.degree.C., the
pressure of the solution is in excess of 900 psig; and the melt
flow rate (MFR) of the isotactic polypropylene fulfills the
following formula:
(MFR/c) .gtoreq. 1.13 - 0.04 (T-220)
in which c is the concentration of the isotactic polypropylene in
the solution, expressed in weight percent and T is the temperature
(.degree.C.) of the solution, and wherein MFR is equal to a numeral
between 2 and 30, inclusive;
2. and extruding said solution abruptly into a region of lower
temperature and pressure. Values of (MFR/c) at least 15 percent
higher than the minimum value defined above are preferred. The most
preferred extrusion temperatures are in the range from 220.degree.
to 235.degree.C. The preferred pressures are those which will
maintain the solution in a single phase condition at the
corresponding temperature and concentration, as depicted in FIG. 2.
It is also preferred that the solution be extruded via a small
pressure letdown chamber just upstream of the terminal extrusion
orifice wherein the pressure is reduced to a value which will yield
a two-phase solution, again as depicted in FIG. 2.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph of the relationship between MFR/c and
temperature.
FIG. 2 is a graph illustrating phase changes encountered under
various conditions of temperature and pressure for solutions of
isotactic polypropylene and trichlorofluoromethane at several
concentrations.
FIG. 3 is a cross-sectional view of a spinneret having a letdown
chamber suitable for spinning transient two-phase solutions,
according to one of the preferred processes of this invention.
FIG. 4 is a graph showing combinations of temperature and pressure
for a blend of isotactic polypropylene and trichlorofluoromethane
when heated in a closed vessel.
FIG. 5 is a diagram of a convex slot shroud, as employed in several
of the Examples hereinafter.
DESCRIPTION OF THE INVENTION
The key relationship between (MFR/c) and extrusion temperature
which appears to govern whether high quality polypropylene
plexifilaments having good morphology or plexifilaments having poor
morphology will be produced, is empirical in nature, and has been
discovered by examining the results of a large number of flash
extrusion experiments. Thus, when flash extrusion of the system
isotactic polypropylene/trichlorofluoromethane was attempted
employing only the teaching of the prior art, the results--
particularly as regards production of high-quality plexifilamentary
products-- appeared to be extremely erratic. Further work included
studies of not only the known prior art variables of concentration,
pressure, and temperature, but also such variables as polymer
source (various manufacturers, various initial MFR's various
molecular weight distributions, etc.) and incorporation of various
additives, and attempts to duplicate deliberately those which might
have been occasionally present adventitiously, as well as a survey
of the affect of a wide variety of surfactant additives. Although
no controlling parameter was found amongst these variables, the
vast majority of the results of these varied experiments fell into
a regular pattern, once the key parameters of (MFR/c) and T were
discovered.
FIG. 1 is a graphical representation of the parameters (MFR/c) and
T depicting the results for some 70 flash extrusion experiments
detailed in the examples included hereinafter. To be sure, a small
hand-full of experiments run under conditions quite close to the
"key relationship boundary line" yield products whose morphology is
predicted incorrectly, possibly indicating that this boundary-- at
least as expressed solely in terms of the (MFR/c) and T
parameters-- has some finite width rather than the infinite
sharpness of a geometrical line. This feature is suggested in FIG.
1 by the shaded band which covers all conditions within 15 percent
of the "key relationship boundary line." However, even within this
boundary region, the morphology of the product is predicted
correctly most of time. In the regions above and below this
boundary region, the products' morphology is correctly predicted by
the present key relationship in the overwhelming majority of cases.
No special significance is attributed to the few exceptions to the
general rule, other than the possibility that the recorded MFR's
for these particular products may have been in error, since some
difficulties with these measurements have occasionally been
experienced.
This key relationship is quite unexpected since it teaches that
successful operation with this system is possible only under
conditions approximately an order of magnitude removed from the
preferred conditions taught in the prior art for other similar
flash spinning systems. For example, at an extrusion temperature of
220.degree.C. (the mid-point of the operable range from
200.degree.-240.degree.C.), the relationship requires that the MFR
of the polymer in solution be at least 1.13 fold greater than the
polymer concentration in the solution expressed in weight percent.
In marked contrast, the art polyolefin flash extrusion procedures
commonly employed polymer whose MFR <<1.0 (e.g., 0.2) at
concentrations of 10 percent and higher, and whose (MFR/c) ratios
would therefore be <<0.1 in contrast to the 1.13 minimum
ratio required for the present trichlorofluoromethane/isotactic
polypropylene system. Furthermore, since solution concentrations of
at least 2 percent polymer, and preferably at least 4 percent
polymer, are required in order to generate a continuous
plexifilamentary product in the flash spinning process (and
concentrations of at least 10 percent are preferred for
commercially attractive processes) this newly discovered key
relationship teaches that polymer of high MFR-- at least 2, and
preferably at least 4-- is required in order to produce high
quality plexifilamentary products from this system. It is
surprising that plexifilamentary products of polymers with such
high MFR's (low molecular weights) continue to exhibit attractive
high tenacities particularly in view of the prior art teachings of
a strong preference for employing polymers of MFRs substantially
less than one.
The isotactic propylene polymer employed in this invention is not
necessarily composed of 100 percent propylene units. The polymer
may have as much as 15 percent by weight of units derived from
other ethylenically unsaturated monomers such as ethylene,
isobutylene, vinyl acetate, or methyl methacrylate. Furthermore,
the polymer may contain some nonisotactic polypropylene units.
Thus, the term "isotactic polypropylene" as used herein refers to
such polymers containing at least 80 percent by weight, of
isotactic polypropylene macromolecules. A further description is
given by Natta et al. in U.S. Pat. No. 3,166,608.
The polymer in the solution to be flash extruded should have a MFR
high enough to satisfy the above-described key relationship at the
particular concentration and solution temperature chosen, but
preferably not substantially in excess of MFR = 30, since otherwise
the physical properties-- particularly the tenacities-- of the
resulting plexifilamentary products drop off to unattractive levels
simultaneously with a deterioration of the morphology of the yarn
(degrees and uniformities of fibrillation). The MFR of the polymer
is determined according to ASTM method 1238T Condition L. Isotactic
polypropylene with MFR meeting the above conditions may be employed
directly in making up the flash spinning solutions or alternatively
and preferably, isotactic polypropylene of lower initial MFR may be
employed and be deliberately thermally degraded to the required MFR
during solution preparation, storage, and transfer to the extrusion
orifice. In either case, the MFR of the isotactic polypropylene in
solution just prior to extrusion is inferred by running the ASTM
test on the quenched and dried (solvent free) plexifilamentary
product produced on flash extrusion.
In this specification "high quality plexifilament" means a
continuous, three-dimensional, interconnected strand or web of
film-fibrils which is highly fibrillated, i.e., is substantially
free of foamy material but not over-fibrillated, i.e., is not
shredded or torn apart, has substantially all its film-fibrils
interconnected at both ends, and is produced without generation of
appreciable quantities of loose particles ("fly"). Such a "high
quality plexifilament" is also described herein as a product having
"good morphology."
To prepare the spinning solution, the polymer and solvent are mixed
by any of a number of known methods. For example, powdered
isotactic polypropylene may be blended with liquid
trichlorofluoromethane at room temperature to form a dispersion.
The resulting dispersion (slurry) may then be heated with stirring
in the vessel which is to serve as a supply reservoir for spinning,
or it may be continuously pumped through a heat exchanger to a
spinneret or spinning cell. In either case, the solution should be
delivered to the spinneret at a temperature of at least
200.degree.C. and at a pressure greater than the two-liquid-phase
boundary pressure described in subsequent paragraphs. For all
spinnable solutions of this invention this pressure is above 900
psig and is well above the vapor pressure of the solvent. This
superautogenous pressure can be created by pressurizing the system
with an inert gas such as nitrogen. The inert gas should preferably
not be mixed with the solution but rather should be present as a
force pressing against it. No upper pressure limit exists, of
course, save those imposed by the equipment design. Alternatively
the required superautogenous pressure can be generated (1) by
mechanical means such as one or more pumps or (2) by heating the
blend to the desired temperature in a vessel "filled" with the
blend such that thermal expansion of the confined blend generates
sufficient pressure to prevent formation of any gas phase above the
solution at the desired extrusion temperature.
Since the pressure on the solution is well above the vapor pressure
of the solvent, abrupt extrusion into an area of substantially
lower temperature and pressure will cause the solution to "flash"
from the container.
Trichlorofluoromethane has only limited solvent power for isotactic
polypropylene, i.e., it dissolves appreciable quantities of polymer
only at temperatures above its normal boiling point and at
super-atmospheric pressures. However, at progressively higher
temperatures the solvent power again decreases (as thermal
expansion tends to decrease the solvent density) and such
"super-hot" flash spinning solutions generally form cloudy
dispersions which, if allowed to stand without adequate agitation,
separate into two distinct layers, one being polymer-rich and the
other being polymer-lean. This "partial dissolution" may be avoided
by applying still higher super-autogenous pressure to the system to
prevent the solvent density decrease and loss of solvent power and
thus maintain a single phase solution. Such single phase solutions
are preferred in order to avoid the undesirable discontinuities
which otherwise could occur in attempting to store, transfer and
extrude a gross two-phase system of nonuniform composition.
However, it has been found desirable, in order to achieve superior
fibrillation of the product, to pass such homogeneous single phase
solutions through a small pressure letdown chamber to form a
transient two-phase solution in the form of an extremely fine
dispersion which promptly exits through the final spinning orifice
before coalescence of the dispersion can occur.
The operation of this single phase solution/two-phase extrusion for
the present trichlorofluoromethane/isotactic polypropylene system
amy be better understood by referring to FIG. 2, where the ordinate
for the graph is temperature, .degree.C.; and the abscissa is gauge
pressure in pounds per square inch (psig.). Absolute pressure
(psia) are 15 psi greater than gauge pressure. Line A of the graph
gives the vapor pressure of the solvent trichlorofluoromethane at
various temperatures. Line B shows the critical temperature of the
solvent (198.degree.C.) while line C shows the critical pressure
(625 psig). Line E shows the temperature limit (200.degree.C.)
above which the polymer/solvent combinations of this invention will
give strong continuously fibrillated products. Line G indicates the
minimum pressure (900 psig) for obtaining strong continuously
fibrillated products.
A family of curves H, J, K and L, corresponding to solution
concentrations of 13 percent, 12 percent, 11 percent, and 10
percent, is also shown in FIG. 2. Each curve represents a series of
pressure/temperature combinations which are herein referred to as
the "two-liquid-phase pressure boundary." To better visualize the
graph one should look for the curve in the family which corresponds
to the solvent/polymer concentration of interest and should then
imagine that the other lines are nonexistent. For example, the
two-liquid-phase pressure boundary for a 10 percent solution of a
given sample of isotactic polypropylene in trichlorofluoromethane
at various temperatures is represented by line L. The system at
equilibrium under all temperature-pressure combinations to the left
of line L consists of two liquid phases: a polymer-rich liquid, and
a polymer-lean liquid. On the other hand, under
temperature-pressure combinations to the right of line L the system
consists of a single liquid phase.
In flash spinning a 10 percent solution of isotactic polypropylene
in trichlorofluoromethane, for example, the solution in the main
reservoir and solution transfer lines upstream of the inlet orifice
to the pressure letdown chamber should have a temperature-pressure
relationship corresponding to a point within the area to the right
of line L. For example, the solution might be maintained at a
temperature of 220.degree.C. and a pressure of 1,600 psig as
indicated by point Y on the graph. Under these conditions the
solution consists of a single liquid phase. When such a solution
passes through a properly sized inlet orifice into the pressure
letdown chamber, its pressure can be made to drop, for example, to
1,200 psig, while the temperature drops only slightly, e.g.,
1.degree. to 2.degree.C., as represented by point Z on the graph.
Under instantaneous conditions at point Z, the solution consists of
two-liquid phases in the form of a very fine dispersion. The
continuous phase is a solution of isotactic polypropylene of
relatively high concentration as compared to the dispersed phase.
The dispersed phase is essentially pure solvent with a very small
amount of polymer dissolved therein. The volume of the letdown
chamber should be selected such that the residence time of the
two-phase solution within the letdown chamber will be sufficiently
brief to avoid separation of the two phases into distinct layers.
In the absence of dispersion-stabilizing treatments, e.g.,
stirring, such residence time is preferably kept below 30 seconds.
Under these preferred conditions, the solution passes through the
final constriction, i.e., the spinneret orifice, into the
atmosphere in a very finely divided dispersed form, and the solvent
evaporates instantaneously giving a highly fibrillated strand of
polypropylene. If the residence time in the letdown zone
substantially exceeds 30 seconds, the two phases are likely to
separate into layers or into large droplets. Commonly a strand
produced under the latter conditions would be discontinuous or
otherwise possess nonuniform morphology.
As will be apparent from FIG. 2, a wide variety of conditions can
be used to obtain the desired highly-fibrillated strand. By
experimentation it has been found that the location of the
two-liquid-phase pressure boundary shifts upward and to the left
when solutions of higher concentration are used and shifts downward
and to the right for lower concentrations. The location of the
two-liquid-phase pressure boundary for a given polymer
concentration is not very sensitive to changes in polymer melt flow
rate (melt flow rate being inversely related to molecular
weight).
The location of the two-liquid-phase pressure boundary may be
established for a given polymer batch and solvent combination by
observing the solution at various temperatures and pressures
through a high-pressure sight glass in an apparatus equipped with a
mechanical pump or other means for providing the necessary
superautogenous pressures. At pressures above the two-liquid-phase
pressure boundary, the solution will be clear; at pressures below
the two-liquid-phase pressure boundary the solution will be cloudy.
The phase boundary (temperature and pressure) for a given set of
conditions is read at the point where incipient cloudiness of the
solution in the sight tube is first observed. When the data have
been collected for a number of temperatures, a graph may be
constructed by plotting the boundary pressure for each temperature
as in line J of FIG. 2. It is desirable to observe the solutions
under static conditions as well as under flow. For this observation
a needle valve can be used in place of the spinneret, and this
valve may be closed while the solution is being observed through
the sight glass. By regulating the flow rate through the spinneret,
further data can be obtained to establish the optimum residence
time for the solution in the pressure letdown zone.
When a relatively insoluble inert gas such as nitrogen is dissolved
in the system, the two-phase boundary line generally shifts
downward and to the right. Although introduction of such a gas
tends to increase the degree of fibrillation of the product, there
are certain practical difficulties which ensue. Since the dissolved
gas causes the two-liquid-phase pressure boundary to move to higher
pressures, equipment which will hold higher pressures is required
in such systems. Furthermore, quantitative regulation of the gas
concentration is difficult. Thus, although batch extrusion
experiments, as illustrated in the examples hereinafter, may for
convenience employ nitrogen gas to maintain a selected
superautogenous pressure during extrusion of the solution,
preferably the gas simply exerts a pressure on the surface of the
solution and dissolution of the gas in the system is minimized by
avoiding stirring of the gas-pressurized system and minimizing the
exposure time of the system to the gas. In order to completely
avoid complications due to variable gas dissolutions, it is
generally preferable to use mechanical means such as pistons or
screw extruders for building up pressures in commercial
processes.
For economic reasons the spinnable concentrations for flash
spinning are advantageously above the level of 10 percent polymer
in solution. However, at very low concentrations, (usually below 2
percent), another phase boundary will be found in which the phase
relationships are reversed from those discussed in the preceding
paragraphs. Thus, in this very low concentration area the dispersed
phase will consist of a small percent polymer in solution while the
continuous phase will consist mainly of clear solvent. At this end
of the concentration scale the pressure boundary curves will move
closer to the autogenous vapor pressure curve A as lower
concentrations are used. However, solutions or dispersions having
such low polymer concentration, i.e., less than 2 percent,
ordinarily do not give continuous fibrillated strands of uniform
morphology and hence are unsuitable in the practice of this
invention. For convenience, an upper polymer concentration level of
20 percent is provided.
In the examples which follow, a batch process is used for preparing
solutions, and a thermal-expansion technique is employed for
generating the required superautogenous pressures. In using this
technique, it is important to charge a sufficient quantity of
polymer and solvent such that thermal expansion of the mixture will
completely fill the autoclave when the temperature reaches some
intermediate value. Further heating of the confined solution will
generate the required superautogenous pressure when the desired
extrusion temperature is reached. The required amount of material
may be closely estimated if the density of the solution is known
for the desired spinning temperature and pressure. Use of a slight
excess of material is recommended, since any excess pressure may be
released by venting a small amount of solution during the heating
operation.
In FIG. 4 pressure is plotted versus temperature for a blend of 10
percent polypropylene and 90 percent trichlorofluoromethane heated
while confined in an autoclave. Isotactic polypropylene weighing,
for example, 2,050 g. is added to a steam jacketed, stirred
autoclave containing a void space of 18,000 ml. The autoclave
containing the polymer is then evacuated to remove the air and
18,450 grams of "Freon-11" trichlorofluoromethane solvent is added
while the autoclave is under vacuum. The autoclave is then closed.
The agitator is turned on and the autoclave heated as rapidly as
possible while a graph of the temperature and pressure is made
during the heat-up cycle.
Line Q of FIG. 4 represents the vapor pressure of solvent at
various temperatures during the first stage of the heating cycle.
Departure of the pressure level from the vapor pressure curve for
"Freon-11" at R defines the temperature and pressure conditions at
the point of "filling" the autoclave, i.e., the point at which the
solvent vapor phase disappears. As the heating is continued, the
pressure rises sharply. If no material is released from the
autoclave the temperature and pressure combinations shown by line S
will be recorded. It should be understood that a family of curves
similar to line S will be generated by charging various amounts of
ingredients. The temperature required for "filling" the autoclave
will increase as the amount of ingredients decreases. Excessive
pressure (due to minor errors in calculation or inaccurate density
values) may be released by bleeding off small portions of the
material from the autoclave from time to time. In order not to
alter the relative quantities of polymer and solvent, it is
desirable that this bleeding not be required until after the
polymer has dissolved, which occurs rapidly at a temperature of
about 110.degree.C. When the correct quantity of ingredients has
been charged, bleeding the autoclave will not be necessary before
reaching a temperature of approximately 180.degree.C. as indicated
in FIG. 4.
When the solution is ready for flash spinning, the agitator is
stopped and the solution is pressurized with nitrogen gas to the
desired extrusion pressure, e.g., a pressure 100 to 200 psig above
the two-phase boundary pressure. Stirring is avoided from this
point on to prevent mixing and dissolution of the nitrogen gas in
the solution. The applied nitrogen pressure within the autoclave is
maintained constant during spinning.
In the following examples and elsewhere in the disclosure, parts
and percentages are by weight unless otherwise indicated.
EXAMPLE I
A series of solutions of isotactic polypropylene and
trichlorofluoromethane was prepared at various concentrations from
several commercial sources of polymer, as described in Table 1A.
These solutions were prepared in a five-gallon autoclave by the
filled-system technique described above. The computed quantities of
polymer and solvent were charged into the autoclave which was then
sealed, and stirring and heating commenced to reach the fill-point
temperature of approximately 160.degree.C. (corresponding to point
R of FIG. 4) in about twenty minutes. Further heating to reach the
spinning temperature of 220.degree.C. required a minimum of about
70 minutes additional time, and even longer heating times were
sometimes employed when additional polymer degradation in solution
was desired. Just prior to extrusion, nitrogen pressure was applied
above the solution to hold the pressure during extrusion above the
single phase boundary line (cf. H, J, K, and L in FIG. 2). A value
of approximately 1,750 psig is preferred. The spinneret assemblies
employed included a pressure letdown chamber as shown at 13 in FIG.
3 and preceded by a letdown orifice 12 and leading to a spinneret
orifice 14 terminating in an exit (slot) shroud 16. All the runs
except No. 6 employed a rectangular slot shroud, i.e., the exit
face is flat and perpendicular to the axis of the cylindrical
spinneret orifice, which is centrally located in the "bottom" of
the slot shroud, as indicated in the FIG. 3 side view. Run No. 6
employed a convex shroud, i.e., the exit face is a spherical
segment such that the ends of the slot are shallower than the
central portion (which is directly in line with the spinneret
axis), as illustrated in FIG. 5. The function of these shrouds is
to spread the expanding vaporizing solution laterally in order to
generate a web-shaped plexifilament. The pertinent dimensions of
the spinnerets employed for each run are tabulated in Table 1B.
The 30 runs recorded in Table 1A were all extruded at
220.degree.C., and therefore should produce "good" and "bad"
morphology products for (MFR/c) ratios above and below 1.13,
respectively. Only five of these runs failed to fit the predicted
morphology pattern and four of these five "exceptions" (runs 2, 4,
9, and 25) occur so close to the boundary line (within .+-. 15
percent) that they do not constitute meaningful "exceptions,"
allowing for the experimental uncertainties in the polymer MFR
data. (Production of a "bad" morphology product in run 24 remains
unexplained). The data for these runs are plotted in FIG. 1. Note
from Table 1A the strong tendency for flexifilaments of good
morphology to exhibit the higher tenacities.
EXAMPLE II
Another series of flash extrusion experiments employing isotactic
polypropylene/trichlorofluoromethane was conducted in a 20-gallon
autoclave employing filling and heating techniques similar to those
described above. However, in order to explore extrusion performance
at higher temperatures, the maximum autoclave solution temperature
for this series was generally held between
170.degree.-200.degree.C. (where polymer degradation rates are not
excessive) and the autoclave was connected to the spinneret by a
heated 186-inch long 1/4-inch diameter transfer line whereby the
solution temperature could be raised rapidly during flow through
the line to extrusion temperatures between
220.degree.-240.degree.C. with minimum exposure time to these
polymer-degrading temperatures. Although precise temperature
control with this experimental system was difficult, data for
higher temperature extrusions were obtained as reported in Table
2A. Points for these runs are also indicated on FIG. 1, and again--
except for three or four possibly significant exceptions-- the
morphologies of the products are as predicted by the (MFR/c)
relationship.
Pertinent data for the spinneret hardware employed in these runs
are given in Table 2B.
EXAMPLE III
Nine 5-gallon autoclave flash extrusion experiments were run by the
procedure of Example I to define the maximum operable polymer MFR,
since high values of this parameter are required in order to exceed
the (MFR/c) limit whenever higher concentrations are employed. All
nine runs employed isotactic polypropylene of initial MFR equal
0.4, and the solutions were held at elevated temperature for
varying periods of time in order to provide varying degrees of
degradation, and hence MFR increases, prior to extrusion. Each
product in this series would be predicted to have good morphology
and high tenacity, since each run (except perhaps for No. 67)
satisfied the required initial conditions of temperature,
concentration, pressure and (MFR/c), as indicated by the data of
Table 3A. However, the results of these experiments (e.g., runs 62,
66, 69) indicate that for polymer MFRs above about 30, polymer
degradation has become so severe that the plexifilament morphology
deteriorates, i.e., the film-fibrils are too weak to prevent web
splitting during the violent flash extrusion process, and yarn
tenacity as measured on plexifilamentary samples twisted to 10 tpi
also falls to lower values. (No immediate explanation is at hand
for run 65, which appears to be an exception to the general
correlation.) Unfortunately, but not surprisingly, the data (e.g.,
runs 61, 68) do not indicate a sharply defined maximum operable
polymer MFR, but simply indicate that MFR's below about 30 are to
be preferred.
The pertinent spinneret hardware parameters for these runs are
indicated in Table 3B. ##SPC1## ##SPC2## ##SPC3## ##SPC4## ##SPC5##
##SPC6##
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