U.S. patent number 3,920,508 [Application Number 05/295,339] was granted by the patent office on 1975-11-18 for polyolefin pulp and process for producing same.
This patent grant is currently assigned to Crown Zellerbach Corporation. Invention is credited to Hayato Yonemori.
United States Patent |
3,920,508 |
Yonemori |
November 18, 1975 |
Polyolefin pulp and process for producing same
Abstract
A polyolefin pulp suitable for papermaking is described which is
formed of a mass of discrete fibers formed of convoluted strands,
the convoluted strands being twisted or wound-up film or sheet-like
elements, the pulp having a drainage factor greater than 1.0
seconds/gram and a compressability constant (N) between about 0.3
and 0.4. Further, a process of manufacturing such fibers by forming
a dispersion (mixture) of a solvent, a polyolefin, a water
dispersing agent for the pololefin fibers to be formed and water
and flashing the mixture through a nozzle. Water is present as a
continuous phase in the mixture. The polyolefin is crystalline, or
partially crystalline, preferably polyethylene, polypropylene,
copolymers of ethylene and propylene, and mixtures thereof. The
fibers thus formed can be easily refined and used for making paper
webs.
Inventors: |
Yonemori; Hayato (Iwakuni,
JA) |
Assignee: |
Crown Zellerbach Corporation
(San Francisco, CA)
|
Family
ID: |
26350963 |
Appl.
No.: |
05/295,339 |
Filed: |
October 5, 1972 |
Foreign Application Priority Data
|
|
|
|
|
Oct 12, 1971 [JA] |
|
|
46-79856 |
Feb 14, 1972 [JA] |
|
|
47-14919 |
|
Current U.S.
Class: |
162/157.5;
162/168.1 |
Current CPC
Class: |
D01D
5/11 (20130101) |
Current International
Class: |
D01D
5/00 (20060101); D01D 5/11 (20060101); D21F
011/00 () |
Field of
Search: |
;162/157R,168
;260/29.6XA,94.9A,94.9F ;264/115,205,13,15 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Bashore; S. Leon
Assistant Examiner: Chin; Peter
Attorney, Agent or Firm: Teigland; Stanley M. Horton; Corwin
R. Howard; Robert E.
Claims
I claim:
1. A process for producing a polyolefin pulp comprising forming a
mixture of a polyolefin, a solvent for the polyolefin at elevated
temperatures, water as the continuous phase, and polyvinyl alcohol
dissolved in the water, the mixture being at a temperature above
the melt dissolution temperature of the polyolefin in the solvent
and at substantially autogeneous pressure, the polyolefin being
present in an amount of from about 0.5 to 15 percent by weight of
the solvent, the polyvinyl alcohol being present in an amount from
about 0.1 to 5 percent by weight of the polyolefin, the solvent
being inert and stable at the mixture temperature and substantially
immiscible in water or forming a polymer solution which is
substantially immiscible in water; passing the mixture through a
nozzle into a zone of lower pressure to vaporize the solvent and
form an aqueous slurry of fibrous polyolefin, the pressure in the
zone being such that the temperature of the mixture falls below the
softening point of the polyolefin, and; refining the aqueous slurry
of fibrous polyolefin into a pulp of discrete fibers.
2. The process of claim 1 wherein the polyolefin is a crystalline
polyolefin selected from the group consisting of polyethylene,
polypropylene, ethylene-propylene copolymers and mixtures
thereof.
3. The process of claim 2 wherein the polyolefin is
polyethylene.
4. The process of claim 3 wherein the molecular weight and
concentration of the polyethylene in the solvent is selected to
provide a solution viscosity at the temperature of the mixture
between about 100 and about 3500 centipoises.
5. The process of claim 1 wherein the solvent to water volume ratio
is between about 0.5 : 1 to about 2 : 1.
6. The process of claim 1 wherein the solvent has a boiling point
lower than the melting range of the polyolefin.
7. A process for producing a polyolefin pulp comprising forming a
mixture at a temperature between about 130.degree.C and about
160.degree.C and under substantially autogeneous pressure of a
crystalline polyolefin, a solvent for the polyolefin at elevated
temperatures, polyvinyl alcohol and water; the polyolefin being
present in an amount up to 15 percent by weight of the solvent, the
solvent to water ratio being between about 0.5 : 1 and about 2 : 1,
the water bieng present as the continuous phase of the mixture the
polyvinyl alcohol being present in an amount up to about 15 percent
by weight of the polyolefin, the solvent having a boiling point
lower than the melting range of the polyolefin and stable at the
mixture temperature; passing the mixture through a nozzle into a
zone of lower pressure to vaporize the solvent and form an aqueous
slurry of fibrous polyolefin, and refining the firbrous polyolefin
slurry into a pulp of discrete fibers.
Description
BACKGROUND OF THE INVENTION
It is known to make fibers of synthetic polymers by extruding melts
or solutions thereof through spinnerets and chopping the continuous
filaments thus formed into short lengths called staple fibers. Such
fibers are characterized by having a very low gas absorption
surface area (less than 1.0 m.sup.2 /gm) which causes a fast
drainage rate and poor formation, and are generally not useful in
making synthetic paper webs.
A method is described in U.S. Pat. No. 2,999,778 for preparing
polymeric particles called "fibrids" which have utility in
synthetic paper webs as a binder. This process comprises injecting
a solution of polymer into a precipitant for the polymer under
conditions of shear to thereby precipitate the fibrid particles.
One difficulty with this process is that large volumes of solvent
and precipitant must be employed, and where the solvent and
precipitant are different materials, a solvent separation problem
is presented. Also, the particles thus formed are of such a size
that while useful as binder particles they have little utility as a
substantial replacement for cellulose fibers in papermaking.
In U.S. Pat. No. 3,081,519 a process for forming continuous
"plexifiliments" which can be chopped into staple lengths is
described. Briefly, the process comprises forming a solution of the
polymer and flashing the solution through an orifice under
conditions such that all the solvent is vaporized and a continuous
filament having an integral three-dimensional netowrk is formed.
This process requires that sufficient energy be supplied to the
solution to effect complete vaporization of the solvent and
precipitation of the polymer. The product obtained can be
spunbonded into a non-woven product; however, it requires chopping
into staple lengths before it can be used for papermaking by
conventional techniques. The fibrous network structure thus
obtained is difficult to separate into discrete fibers by refining,
and discrete fibers that are obtained upon refining are not very
satisfactory for papermaking purposes because of the presence of
unrefinable chunks of polymer material caused by the fused
intersections in the integral three dimensional network.
A process similar to that of U.S. Pat. No. 3,081,519 is described
in German Offenlegungsschrift No. 1,958,609. This latter patent
states that at lower polymer concentrations discontinuous fibrous
material may be obtained although there is no specific teaching of
forming such fibers. Also, the economics of going to a very low
polymer concentration is not satisfactory.
A process is described in British Pat. No. 1,262,531 which is
similar to that of U.S. Pat. No. 3,081,519 but wherein a
surface-active agent is employed in the polymer solution in order
to form a product called a "microflake aggregation" which can be
separated into individual microflakes by beating. The use of a
surface-active agent even in small amounts becomes quite expensive
and during formation of a paper web on a paper machine presents a
foaming problem. Also, surface-active agents weaken paper sheets
formed from blends with cellulose fibers, probably due to
degradation of the cellulose bonds by the surface-active agent.
Furthermore, the energy requirements of the process are high as
sufficient energy must be imparted to the polymer solution to
effect complete vaporization of the solvent, and at the
temperatures thus required there is a tendency for a
plexifilamentary product to form.
A process of forming fibers is described in German
Offenlegungsschrift No. 2,121,512 wherein an emulsion of a polymer
solution in water is formed and flashed at a relatively high
temperature and pressure through an orifice to form fibers. Water
is present as a continuous phase and is preferably present in
amounts greater than 200 volume percent of the polymer solution.
Surface-active agents are preferably employed in order to form a
stable emulsion. The emulsion particle size is a critical factor.
This latter process requires the presence of a large amount of
water which must be heated thus increasing the energy requirements
of the system and at the high polymer concentration and high
temperatures described there is a tendency toward plexifilament
formation or the formation of fibrous materials which cannot be
easily refined into fibers suitable for papermaking by the
waterlaying technique. The presence of surface-active agents causes
the same deficiencies previously mentioned. Also controlling the
emulsion particle size within the critical limits set forth is a
difficult task.
A process similar to that of German Offenlegungsschrift No.
2,121,512 is described in German Offenlegungsschrift No. 2,144,409.
In this latter process, a smaller amount of water can be employed,
generally approximately equal in volume to the volume of the
polymer solution. Relatively high temperatures and pressures are
described which tend to form a plexifilament or a fibrous product
that is difficult to refine or separate into discrete fibers. The
process requires the presence of a material which will infiltrate a
portion of the water within the polymer solution particles. The
present of such material in the large quantities described may
detrimentally affect the strength properties of the resulting
fibers, and the process generally suffers from the same
deficiencies discussed previously with regard to German
Offenlegungsschrift No. 2,121,512.
Processes are described in German Offenlegungsschrift No. 2,147,462
and U.S. Pat. No. 3,402,231 wherein a dispersion of molten polymer
in water is prepared and flashed to fibers. In U.S. Pat. No.
3,402,231 no solvent is present and in German Offenlegungsschrift
No. 2,147,461 either no solvent is present or a small amount of
solvent is present. These processes suffer from the large
difficulty of forming a dispersion of molten polymer in water, and
also must generally start with a preformed polymer rather than a
polymer solution or slurry in an organic solvent which is the usual
direct product of a polymerization procedure.
Finally, in French Pat. No. 1,350,931 a process for preparing
fibers is described wherein a dispersion of water in molten polymer
is flashed. No solvent is present in the process, and the process
suffers from the same deficiencies as previously described for
German Offenlegunsschrift No. 2,147,461 and U.S. Pat. No.
3,402,231.
BRIEF DESCRIPTION OF PRESENT INVENTION
The present invention has as one of its objects providing a pulp of
discrete polyolefin fibers that are especially suitable for making
synthetic papers webs by the water-laying technique.
The present invention has as another of its objects providing a
process for forming such a pulp.
Briefly, the pulp produced by the present invention can be easily
formed into paper webs by the conventional water laying technique
or other conventional techniques, either by itself or in admixture
with conventional cellulose papermaking pulp. The pulp has a
drainage factor greater than 1.0 second / gram and a
compressability constant between 0.3 and 0.4.
The present process comprises forming a mixture of a polyolefin, a
solvent for the polyolefin at elevated temperatures, a polymeric
water dispersing agents for the polyolefin fibers to be formed and
water at a temperature above the melt dissolution temperature of
the polyolefin in the solvent and at a substantially autogeneous
pressure, the water being present in a sufficient amount to form
the continuous phase in the mixture, passing the mixture through a
nozzle into a zone of lower pressure to form an aqueous slurry of
fibrous polyolefin, and refining the aqueous slurry of fibrous
polyolefin into a pulp of discrete fibers.
Various aspects of the invention are illustrated in the drawing
herein:
FIG. 1 is a diagrammatic view of examplary apparatus which may be
employed in the present invention to produce fibers.
FIG. 2 is a diagrammatical view of the apparatus for receiving such
fibers as they are produced, separating the vaporized solvent
therefrom and for beating or refining such fibers.
FIG. 3 is a cross-sectional view of a preferred precipitation
nozzle as illustrated generally at 6 in FIG. 1.
FIG. 4 is a 500 times magnification of typical fibers of the
invention; and
FIG. 5 is a 10,000 times magnification of the same typical
fibers.
The fibers produced in accordance with this invention have average
lengths between 0.5 mm and 10 mm (as measured by TAPPI Test T 232
SU 68) when prepared for use as a substitute for normal cellulose
fibers. For speciality uses they may be prepared in average length
longer than 10 mm and for some uses fibers having average lengths
up to 100 mm or longer may be prepared. They have an average
coarseness (as measured by TAPPI Test 234 SU 67) of between about 1
and 10 decigrex (mg/100 m).
After refining, the fibers of the present invention are of such a
size that less than about 10 percent by weight of the fibers are
retained on a 20 mesh Tyler Standard screen but at least about 25
percent by weight are retained on a 65 mesh screen and preferably
at least about 25 percent by weight are retained on a 35 mesh
screen. Typically, the weight average length of the fibers after
refining is between about 1.4 and 3.0 mm, the weight average
coarseness is typically between about 3.3 and 8.0 decigrex, and the
weight average length to coarseness is typically 0.37 to
0.51:1.
The fibers of this invention are predominantly made up of sheet or
film like elements which are rolled or twisted into convoluted
strands (visible at 500 times magnification) having a diameter
betwen about 0.5 and 30.mu. and having lenths similar to the fiber
length. When congregated together in a mass or pulp these
convoluted strands are mechanically entertwined with substantially
no inter-strand bonds being present in distinction to the integral
three dimensional network of plexifilaments and other products.
There may however be some intra-strand interconnection as in the
case where the orginal film or sheet was torn and the dangling
portions rolled or twisted into separate strands with the untorn
portion of the orignal film or sheet still connecting the
strands.
Morphologically, the fibers of the present invention appear quite
similar to those described in U.S. pat. application No. 257,609
(filed May 30, 1972). In addition to the convoluted strands or
rolls visible at 500 times magnification, the fibers have a
characteristic "shark-skin" or "pebble" texture at 10.000 times
magnification. A large number of fibers from any given sample will
exhibit grooves or valleys which extend in the direction of the
roll or strand with wrinkles extending transversely thereto between
the grooves.
The convoluted strand or roll structure may be seen in FIG. 4 which
is a 500 times magnification of the fibers produced in Example 10,
run 1. The shark-skin and pebbled appearance may be seen in FIG. 5
which is a 10,000 times magnification of the same fibers.
The surface area of these fibers may range from 2 to 150 m.sup.2 /g
as measured by gas adsorption technique on freeze dried
samples.
Paper-like sheets may be produced from these fibers having a
tensile strength, both wet and dry, between 0.2 and 5 grams per
denier.
While the fibers produced under this invention are produced as an
entangled mass or pulp of the convoluted strands just described,
these strands can be separated from one another since they are not
bonded together, and in such cases these individual convoluted
strands may be considered as "fibers" themselves.
While the fibers produced by the present process are similar
morphologically to the fibers produced by the process described in
aformentioned U.S. pat. application Ser. No. 257,609 they have
several unique features which make them even more suitable for use
in manufacturing paper. Many of these unique properties are related
to the drainage or filtration resistance characteristics of these
fibers.
While the surface area of the fibers of the present process, as
measured by gas adsorption techniques, is quite similar to the
surface area of the fibers produced in the aforementioned U.S.
patent application, the present fibers have a more favorable
hydrodynamic specific surface area. This latter parameter is more
closely related to the drainage characteristic of fibers to be used
in papermaking. The larger the hydrodynamic specific surface are
the more fibrillated the fibers which leads to improved strength
properties of the web or sheet produced therefrom due to the larger
interfiber contact area which can be bonded. Unbeaten or unrefined
cellulose fibers will typically have a hydrodynamic specific
surface area of about 1.0 m.sup.2 /gm and, upon refining can be as
high as 10 to 25 m.sup.2 /gm. The polyolefin fibers produced by the
process of the aforementioned U.S. patent application Ser. No.
257,609 have a hydrodynamic specific surface area less than 1.0
m.sup.2 /gm, typically between 0.7 and 0.9 m.sup.2 /gm. The
polyolefin fibers of the present invention have a hydrodynamic
specific surface area much more like unbeaten cellulose fibers,
i.e., greater than 1.0 m.sup.2 /gm and typically between 1.0 and
2.0 m.sup.2 /gm.
Determination of hydrodynamic specific surface area is determined
in accordance with the procedures described in the article "The
Filtration Resistance of Pulp Slurries". W. L. Ingmanson et. al.,
TAPPI 37, No. 11 : pp. 523-534 (1954). Equations 9 and 10 on pages
515 and 526 of this article were employed in determining the
"hydrodynamic" specific surface area (S) discussed herein.
A further measure of the drainage characteristics of fibers is
compressability constant (N) as determined from the slope of the
curve obtained in making a logarithmic plot of c versus p in the
relationship.
c = Mp.sup.N
wherein c is the apparent pad density in grams/cubic centimeters, p
is the compacting pressure in grams per square centimeter, and M
and N are compressibility constants. Reference is made to equation
(8) on page 525 of the above cited TAPPI article.
The compressibility constant of N of cellulosic fibers is typically
between 0.3 and 0.4 whereas the compressibility constant N of
dacron, orlon and nylon staple fibers is typically between 0.2 and
0.3. What this means is that cellulose fibers are more compressible
than synthetic staple fibers which provides improved bonding
potential and stronger paper webs. The fibers produced by the
aforementioned U.S. patent application Ser. No. 257,609 have a
compressibility constant N similar to staple fibers (i.e., between
about 0.2 and 0.3), whereas the polyolefin fibers produced by the
present process have a compressibility constant N between 0.3 and
0.4 which is similar to cellulose fibers.
The drainage time of the fibers produced by the present process is
also more favorable for papermaking than the drainage time of the
fibers produced by the process described in the aforementioned U.S.
pat. application Ser. No. 257,609. Drainage time is measured by
introducing 400 ml of a 0.5 percent consistency slurry of fibers
into the standard sheet mold described in TAPPI Test T 205 M-58
having a 150 mesh stainless steel wire screen in the bottom thereof
and having water covering the screen prior to introduction of the
fiber slurry. Water is added up to the mark in the sheet mold. The
slurry is agitated by four up and down strokes of the standard
stirrer. The valve on the sheet mold is opened and the water
drained from the mold. The time between opening the valve and the
first sound of air suction through the handsheet mat deposited on
the forming screen is recorded on a stop watch and is reported as
the drainage time in seconds.
The polyolefin fibers produced by the process of the aformention
U.S. patent application Ser. No. 257,609 typically have drainage
times of 5 to 6 seconds, whereas the fibers of the present
invention have a higher drainage time of between 6 and 8 seconds.
This slower drainage is desirable since it permits better formation
to occur on a paper machine and is indicative of better
fibrillation and hence better bondability.
A more accurate characterization of drainage characteristics than
drainage time, and one that is highly correlated to the
hydrodynamic surface area, is the drainage factor. The drainage
factor for the present fibers is greater than about 1.0 and
typically ranges up to about 3.0 seconds per gram or higher. The
drainage factor of the fibers produced by U.S. patent application
Ser. No. 257,609 is generally between about 0.2 and 0.9
seconds/gram. The fibers produced by the examples of German
Offenlegungsschrift No. 2,121,512, even when treated to render them
water dispersible, exhibit a drainage factor less than about 0.8
second/gram and as low as about 0.02 second/gram. Drainage factor
is determined substantially in accordance with TAPPI Test T221
OS-63 with a slight modification in the method of calculation.
Briefly, approximately ten grams of a fiber sample is weighed and
dispersed in water. The slurry is then added to the standard sheet
mold and water added to the mark. The slurry is stirred by four up
and down strokes of the standard stirrer, which is then removed.
The water temperature in the mold is measured and the drainage
valve opened. The time between the opening of the valve and the
first sound of suction noted. The procedure is repeated with water
only (no fiber) in the sheet mold and the temperature and drainage
time noted. The drainage factor in seconds per gram is then
calculated as follows: ##EQU1## where DF = drainage factor,
seconds/gram
D = drainage time with pulp in mold, seconds
d = drainage time without pulp in mold, seconds
V.sub.T = viscosity of water at temperature T
w = weight of fibers employed in test, grams
The quantity (1/V.sub.T - 1) is tabulated in the aforementioned
TAPPI Test T221 OS-63. This quantity is multiplied by 0.3 which has
been empirically determined for the present fibers.
It has been found that fibers having the desirable characteristics
for papermaking just described can be made by the selection of
certain specific process parameters. If these parameters are not
observed, discrete fibers satisfactory for papermaking by
waterlaying may not be obtained and, in many instances, only
continuous filaments which are difficult or impossible to refine
will be obtained.
Turning now to the process for producing the abovedescribed fibers
a description of one suitable form of apparatus will first be
described.
Autoclave 1, illustrated in FIG. 1, is equipped with stirrer 2 and
valve 3 to supply inert gas or water for preparing the dispersion.
The autoclave is jacketed whereby heating fluid may be used to heat
the contents thereof. Autoclave 1 is also provided with tubular
conduit 4 having an open end inside of the autoclave near its
bottom, and extending therefrom to the exterior of the autoclave.
At the outside end of conduit 4 is shut-off valve 5, constituting a
ball cock valve, to which is connected precipitation nozzle 6. As
seen more clearly from FIG. 3, precipitation nozzle 6 constitutes a
section of tubular conduit 4 and being connected therewith through
valve 5. Precipitation nozzle 6 in turn is connected through
post-precipitation transfer conduit 7 to vaporization vessel 8 as
depicted in FIG. 3. Vaporization vessel 8 constitutes a cyclone
having a conduit 9 for removal of vaporized solvent and a conduit
10 through which fibers may drop to disc refiner 11; alternatively,
other commonly available attrition or beating mills may be used.
Vaporization vessel 8 is also equipped with spray means 12 for
spraying water onto the fibers discharged into such vessel. The
sprayed water is desirably at a temperature sufficiently high
enough not to cause condensation of the solvent vapors moving
upwards to conduit 9.
Autoclave 1 is also provided with a discharge valve 13,
constituting a ball cock valve, at the bottom thereof to which is
connected a short precipitation nozzle 14.
In general operation of this invention using the exemplified
apparatus the polymer and the solvent therefor may be introduced
into autoclave 1 and the polymer dissolved in the solvent by
heating and stirring. Water may then be introduced with stirring to
form a dispersion with the polymer solution as the discontinuous
phase and the water as the continuous phase. A water dispersing
agent for the fibers to be formed is also added to the contents of
the autoclave; most advantageously the agent is added with the
water. Alternatively, the water may be added first followed by
addition of the solution or solvent and polymer thereto.
The pressure maintained in the vessel is substantially autogeneous.
If substantially higher pressures are employed poor fiber formation
results, i.e., fibrous material is formed which is difficult to
refine into satisfactory papermaking fibers.
The dispersion thus formed is maintained under pressure tight
conditions in the autoclave and heated to a temperature
sufficiently high to maintain the polymer dissolved in the solvent,
but no higher than about 160.degree.C. If the temperature exceeds
about 160.degree.C there is a tendency for a fibrous product to be
formed which cannot be easily refined into fibers suitable for
papermaking. Preferably, the temperature is between about
130.degree.C and 160.degree.C. The solvent selected must be stable
at these temperatures. Thereupon shut-off valve 5 may be opened and
by the pressure head inside the autocalve the dispersion therein
will be forced rapidly through conduit 4 and thence through
precipitation nozzle 5. During passage of the dispersion through
conduit 4 and precipitation nozzle 5 the pressure on the dispersion
becomes reduced which thus causes violent vaporization of the
solvent. The loss of heat effected by this vaporization causes the
temperature of the dispersion to drop. This drop in temperature
lowers the solubility of the polymer in the solvent and the loss of
solvent through vaporization also decreases the amount of polymer
that may remain dissolved. Consequently the polymer precipitates as
fibers as the dispersion passes through conduit 4 and out
precipitation nozzle 6. Agitation of the dispersion is maintained
throughout the operation as otherwise the solution phase and water
would rapidly separate.
Upon discharge from precipitation nozzle 6 through conduit 7 into
vaporization vessel 8, which is maintained at a pressure
substantially lower than that existing in conduit 4 and preferably
at atmospheric or subatmospheric pressure, substantially all of the
solvent vaporizes leaving the fibers dispersed as a pulp in the
water. The pulp may be in the form of a "noodle" of fibers losely
aggregated together. Free solvent vapor is removed via conduit 9
and may thereafter be condensed for reuse. Desirably a spray of
water is introduced through spray means 12 onto the dispersed
fibers to inhibit agglomeration of the fibers and to facilitate
refining thereof. The temperature of the spray should be high
enough to avoid condensation of the vaporized solvent.
The fibers are then beaten or refined to reduce or adjust the fiber
length of the material as to desired to give an appropriate fiber
length distribution and degree of fibrillation for the particular
desired end use.
Following formation of the fibers they may be treated with an
additional amount of water dispersing agent. This optional
treatment is supplemental to the addition of the water dispersing
agent to the dispersion prior to flashing. This may be conveniently
done by incorporating the agent in the water which may be sprayed
on the fibers by spray means 12 in the vaporization vessel 8, or by
directly adding the agent to the fibers in the refiner.
For some uses of the fibers of this invention, such as their use in
non-wovens, textile thread manufacture, insulation material, oil
absorption material, etc., it may not be necessary to beat or
otherwise cut the fibers.
Any crystaline polyolefin may be used in accordance with the
present invention to form fibers provided that a suitable solvent
may be found to dissolve the polymer. Of particular importance are
polyethylene and crystalline or predominantly crystalline
polypropylene, ethylene propylene copolymers, and mixtures thereof.
Additionally, polybutenes, polymethyl pentenes, may be desirable
polymers in the practice of this invention.
Polyethylene is the preferred polyolefin employed in the present
invention, and desirably is a low pressure polyethylene having a
viscosity average molecular weight range of 20,000 to 2,000,000.
The most advantageous molecular weight range for polyethylene is
found to be between about 25,000 and 200,000 as this material has
the viscosity and other properties which permit the most economical
manufacture of good quality fibers under this invention. The
preferred polyethylene has an intrinsic viscosity between about
0.85 and 35 and most desirably between about 1.0 and 5.3.
For polypropylene, the viscosity average molecular weight is
preferably between 100,000 and 4,000,000 and most desirably betwen
140,000 and 650,000. The preferred polypropylene has an intrinsic
viscosity between about 1 and 20 and most disirably between about
1.3 and 4.3 for the same reasons indicated for the most desirable
polyethylene range.
The viscosity average molecular weights referred to herein are
determined by first measuring the specific viscosity of the
polyolefin in decolin at 135.degree.C, using Ubbelohde No. 50 or 75
viscometers. The viscosity average molecular weight is then
determined by the relationship:
(.eta.) = K M.sub.v.sup.a
(.eta.) = intrinsic viscosity, and is determined from specific
viscosity by the Schultz and the Blaschke equation.
K = constant, from literature (2.74 .times. 10.sup.-.sup.4 for
polyethylene)
a = constant, from literature (0.81 for polyethylene)
The polyolefin or other polymer employed in practicing the present
process may have been preformed, i.e., previously prepared in the
form of dried powders or pellets, or, preferably, is prepared as an
integral part of the present process. It is preferred to prepare
the polyolefin solution by a solution polymerization process.
Alternatively, a slurry process may be employed and the slurry
heated above the melt dissolution temperature to effect
solution.
Generally, the solvent may be selected from any substituted or
unsubstituted aliphatic, aromatic or cyclic hydrocarbon which is a
solvent for the polymer employed at the temperatures utilized in
the process and which does not decompose at the temperatures
utilized, which is relatively inert under the conditions of
operation and which is substantially immiscible in water or forms a
polymer solution which is substantially immiscible in water. The
solvent should have a boiling point at atmopsheric pressure less
than the softening point of the polyolefin and deisrably in the
range of about 30.degree.C to 120.degree.C. for polyethylene and
polypropylene. The solvent may be liquid or gaseous at room
temperature and atmospheric pressure but preferably is liquid.
Among the solvents which may be utilized are aromatic solvents,
e.g., benzene and toluene; aliphatic hydrocarbons, e.g., pentane,
hexane, heptane, octane and their isomers and homologues, alicyclic
hydrocarbons, e.g., cyclohexane, cyclohexene and methycyclohexane;
halogenated hydrocarbons, e.g., chlorobenzene, carbon
tetrachloride, chloform, ethyl chloride, methyl chloride; alcohols;
esters; ethers; ketones; nitriles; amides; fluorinated compounds
e.g., fluorohydrocarbons; sulfur dioxide; nitromethane; and
mixtures of the above solvents.
One of the features of the present invention is that it has been
found that it is not necessary to form a stable "emulsion" thereby
eliminating the necessity for emulsifiers to be used. However, the
present invention does contemplate the employment of agents in the
mixture to impart water dispersibility to the fibrous polymer.
These agents are preferably water-soluble or partially
water-soluble polyhydroxylated, polymeric materials which are
substantially non-foaming in aqueous slurries at the concentrations
employed. By "polymeric" we mean polymers preferably having a
molecular weight in excess of about 1000. By "polyhydroxylated" we
mean polymers having numerous hydroxyl groups distributed along or
pendent from the polymer chain rather than merely terminal hydroxyl
groups. However, polymers having other hydrophilic moieties such as
amine groups, acid groups and salts and esters thereof distributed
along or pendent from the polymer chain may be employed. Some of
these agents may be technically classified as "emulsifiers", but
they are employed in an amount sufficient to impart the requisite
degree of water dispersiblity to the fibers to be formed and not in
the amounts generally required to form a stable emulsion. The
agents are desirably substantially non-foaming in aqueous slurries
at the concentration employed while most emulsifiers cause foaming
if employed in an amount sufficient to impart a satisfactory degree
of water dispersibility to the fibers, and they are preferably
polymeric materials since such materials resist removal from the
fibers in squeous slurries.
The amount of water-dispersing agent employed may range from about
0.2 to about 15 percent by weight preferably from about 0.1 to
about 5 percent by weight, and most preferably between about 0.7
and about 2.5 percent as shown by the examples below.
The preferred water-dispersing agent is a water soluble polyvinyl
alcohol having a degree of hydrolysis greater than about 77 percent
and preferably greater than about 85 percent, and having a
viscosity (in a 4 percent aqueous solution at 20.degree.C) greater
than about 2 centipoises. The polyvinyl alcohol is preferably added
with the water as a solution therein at the time the mixture is
formed. Illustrative of other water-dispersing agents that may be
employed are polyacrylic acid, polyacrylates, gelatin, casein,
cationic guar gum, cationic starch, potato starch, cellulose
derivatives such as carboxyethyl and carboxymethyl polymeric amines
and Lytron 820 (a stryrene-maleic acid copolymer)
The phase "water-dispersing agent", as stated above, means an agent
which renders the polyolefin fibers water-dispersible. Since
polyolefins are normally hydrophobic, fibers made therefrom cannot
be employed in papermaking by the water-laying techniques unless
they are rendered water-dispersible by the agent.
To measure the extent to which fibers are dispersible in water, a
"dispersibility index" may be measured. To obtain a numerical value
for the dispersibility index, 2 grams of fiber (dry weight) is
dispersed in 400 ml water (total volume) in a Waring Blender at top
speed for 5 seconds. The resulting fiber slurry is placed in a 500
ml graduated cylinder, inverted four times and placed on a flat
table top. The volume of clear water under the fiber slurry is
recorded after 10, 20, 30, 40, 50, 60, 80, and 120 seconds. The
values are summed, and the sum divided by 4 to give the
dispersibility index. The lower the number, the better
dispersibility. To form an adequate sheet from the fiber by
conventional papermaking water laying techniques, it is desirable
that the dispersibility index number be below 350, and, preferably,
below 300. The fibers of the present invention typically have a
dispersibility index well below 300.
While it is not necessary to the present invention to add a
surfactant to the dispersion to form a `stable` emulsion, a
surfactant may optionally be added in addition to the water
dispersing agent previously discussed. Such surfactants may be
nonionic, cationic or amphoteric and are preferably of the type
that enchance an oil-in-water type emulsion i.e., ones having a
relatively high (greater than about 7.0) HLB
(hydrophilic-lipophilic balance) value. If such a surfactant is
employed and the fibers produced are to be used for making paper
webs by the water laying technique, it is desirable to remove the
surfactant from the fibers prior to web formation by washing in
order to prevent foaming.
The polymer, solvent and water dispersing agent, selected as
described above, should provide, upon sufficient agitation, a
uniformly dispersed solution phase (solvent plus dissolved polymer)
in the water phase (preferably containing the water-dispersing
agent dissolved therein) at the temperatures and pressures of
operation.
For practical operation utilizing preformed solid polymer the
polymer is first dissolved in the solvent utilizing heat and
agitation where necessary. The water is then added with agitation
to form the dispersion. The water-dispersing agent is conveniently
incorporated into the water prior to its addition to the dissolved
polymer. Alternatively, the solution may be added to the water.
However, notwithstanding the batch process embodiment previously
exemplified, it is preferred and advantageous to carry out this
invention in a continuous process together with the polymerization
process for the polymer. Polymerization of the polymer may be
carried out by conventional means in a separate vessel. If a
solution polymerization process such as that used for polyolefins
is employed, then the resulting polymer solution may be fed
directly to a dispersion forming essel or autoclave, with the
adjustment of the solution concentration and treatment of the
residual polymerization catalyst as may be necessary. The water may
be added to the dispersion forming vessel, in the manner previously
described, on a continuous basis with stirring to maintain the
dispersion. The dispersion forming vessel may be heated to maintain
the dispersion at the desired temperature and pressure for
discharge to a zone of lower pressure to form fibers in the same
general manner as described for the batch process embodiment.
If a slurry polymerization process, such as that used for
polyolefins, is employed, the above described process may be
employed with the desirable modification that the polymer
suspension formed is heated to form a polymer solution prior to its
introduction into the dispersion forming vessel, preferably by
feeding the slurry from the polymerization vessel to an
intermediate heated vessel prior to feeding to the dispersion
forming vessel.
As a further modification, the dispersion ingredients may be mixed
by in-line mixing devices prior to the nozzle; preferably the
polyolefin solution and water containing the water dispersing agent
would be the two streams brought together.
The viscosity of the polymer solution is a variable which has an
important influence on character and quality of the fibers
produced, such as their length, thickness and degree of
entanglement. The viscosity of the polymer solution is related to
both the concentration of polymer and its molecular weight. The
viscosity of the polymer solution increases with the concentration
and the molecular weight (or intrinsic viscosity) of the polymer
selected; therefore the viscosity can be adjusted by appropriate
selection of polymer molecular weight and by adjusting the
concentration of the polymer solution.
The viscosity of the solution should be low enough so that the
solution may be conveniently formed into a dispersion with the
water. If the viscosity is too high a good dispersion is difficult
to form, flow problems are encountered and the product may be a
thick ropy mass rather than the desired fibrous material. For
satisfactory operation the viscosity of the polymer solution under
the temperature and pressure of operation with polyethylene as the
polymer is desirably below 3500 centipoises for longer nozzles and
desirably below 500 to 1000 centipoises for shorter nozzles. The
viscosity of the solution should be greater than about 100
centipoises in order to form thin, well fibrillated fibers of
polyethylene.
Fibers may be produced when the polymer employed is 0.5 percent by
weight of the solvent or even lower. However it is generally
desirable to utilize concentrations higher than 0.5 percent by
weight because the properties of the fibers are generally better
when a more concentrated solution is employed. Additionally, higher
polymer solution concentrations are more economical because the
amount of solvent required for production of a given amount of
fiber is less and the amount of heat required for vaporization
thereof is correspondingly decreased. In general the concentration
may be selected from the range of 0.5 to 15 percent by weight and
preferably between 3.5 and 15 percent by weight. The practical
upper limit of concentration is determined based upon solution
viscosity as previously mentioned. The preferred concentration
range for polyethylene and polypropylene is between 25 and 100
grams per liter of solvent, with a concentration between around 50
and 100 grams per liter being especially useful.
Another variable which greatly influences the character of fibers,
particularly the length, thickness and strength of the fibers and
the extent to which they are entangled, is the ratio of solvent to
water which is employed. For a given polymer, polymer concentration
in the solvent and conditions of precipitation, the higher the
ratio of solvent to water, the longer, thicker and more entangled
are the fibers produced. In some cases if the ratio of
solvent:water is too high and at the same time where the polymer
solution is above certain concentrations, then the product which is
produced may be so thick and entangled that it is difficult to
refine or otherwise treat them in order to produce fibers having
desirable properties. If the ratio of solvent to water is too high,
the fibers produced may be undesirably weak utilizing certain
polymer concentrations, and the process also becomes
uneconomical.
In general the ratio of solvent to water on a volume basis may be
selected from the range of 0.5 : 1 to 2 : 1, preferably between
about 0.5 : 1 and 1 : 1. The ratio of solvent to water is desirably
low enough so that the water contributes sufficient sensible heat
(enthalpy) to the dispersion so that the total sensible heat of the
dispersion is adequate to vaporize substantially all of the good
solvent upon flashing, at the temperature and pressure
differentials employed in the flashing.
Yet another variable which affects the character of the fibers
produced relates to the conditions under which precipitation of the
fibers takes place. The nozzle through which the dispersion is
discharged must provide a constriction on the flow of the
dispersion therethrough to establish adequate shear stress in the
dispersion so as to aid orientation of the polyolefin molecules.
The minimum shear stress required to produce adequate fibers is
dependent upon a number of variables, including the type and
molecular weight of the polymer, concentration of the polymer
solution and the ratio of solvent to water, as previously
discussed. The shear stress can be adjusted by appropriate
selection of the therethrough. size, e.g., diameter if a circular
configuration is used, and length of the precipitation nozzle and
any associated conduit communicating therewith which imparts shear
action on the suspension discharged therfethrough.
For polyolefins which crystallize more rapidly, such as high
density polyethylene, a relatively shorter period of shear stress
may be employed. In the case of polyethylene, for example, fibers
may be produced simply by discharging the dispersion directly
through a circular nozzle 2 millimeters in diameter and 2
millimeters long, as for example through the precipitation nozzle
at the bottom of autoclave 1 in the exemplified apparatus. In fact
sufficient shear stress may be produced simply by throttling the
dispersion through a partially opened valve having an annular
port.
On the other hand for a polymer which crystallizes more slowly,
such as polypropylene, it may be necessary in order to produce
desirable fibers to discharge the dispersion through a fairly long
shear zone such as small, long conduit 4 in the exemplified
apparatus and then through a yet smaller shear zone such as
precipitation nozzle 6 in order to creat sufficient shear force or
turbulence on the polymer prior to and during its precipitation. In
the depicted apparatus there is a substantial pressure drop along
conduit 4 during discharge. However there should still be a
substantial pressure drop across nozzle 6, perphas 5 atmospheres or
higher, in order to maintain an adequately high temperature in
conduit 4 to prevent premature precipitation of the polymer on the
walls of the conduit or of nozzle 6.
The temperature of the dispersion in the vessel should be
maintained high enough so that when it is discharged rapidly
through the precipitation nozzle into the zone of reduced pressure
substantially all of the solvent will vaporize but the temperature
employed should not be so high as to cause any substantial
vaporization of the water. Additionally the pressure in the vessel
should be high enough to force the dispersion through the
precipitation zone with sufficient velocity to create adequate
turbulence and shear action to form desirable fibers. The
autogeneous pressure of the confined vapor of the dispersion is the
preferred pressure employed. Preferably the pressure is between 6
and 15 kg/cm.sup.2 .
In the case of polyethylene and polypropylene in hexane as the
solvent and with water as the continuous phase, the temperature in
the vessel is desirably maintained between 130.degree.C and
160.degree.C, preferably about 140.degree. to 150.degree.C, prior
to discharge of the dispersion through the precipitation zone. The
autogeneous pressure developed by the dispersion at this
temperature range creates the most desirable pressure to force the
dispersion through the precipitation zone, such as through conduit
4 and nozzle 6, at a velocity and residence time in the nozzle
sufficient to create adequate shear stress for good fiber
production.
If a pressure substantially higher than autogeneous (say, greater
than about 20 Kg/cm.sup.2) is employed the fibers are not as
suitable for papermaking probably due to the high velocity and low
residence time in the nozzle. It should be noted that the
"autogeneous" pressure may include a small partial pressure
developed by residual monomer if the process is integrated with the
polymerization process. The sensible heat in the dispersion at this
temperature range is also adequate to vaporize substantially all of
the good solvent when the dispersion is discharged into atmospheric
pressure. The pressure is desirably maintained constant during
flashing by introduction of an inert gas such as nitrogen into the
vapor space over the dispersion in the vessel.
Where a precipitation nozzle of relatively small cross-section is
employed at the end of a larger cross-section shear zone conduit,
it is desirable that the pressure of the dispersion just prior to
entry into the nozzle is maintained high enough so that the
temperature of the dispersion is above the dissolution temperature
of the polymer so that it does not precipitate prematurely on the
walls of the conduit. In practice the pressure is usually 5
atmospheres and higher for polyethylene and polypropylene.
The pressure in the zone of reduced pressure (e.g., varporization
vessel 8) should be low enough so that the temperature of the
dispersion upon flashing falls below the melting or softening point
of the polymer. This pressure is usually atmospheric pressure or
lower, preferably about 1 kg/cm.sup.2 . The dispersion may be
flashed into the atmosphere or into a gas, preferably an inert gas
such as nitrogen. Optionally but less desirably if the pressure
gradient is great enough the dispersion could be flashed directly
into a liquid maintained under low pressure and at a temperature
above the boiling temperature for the solvent but below the boiling
temperature for water and the softening temperature of the
polymer.
Thus in the exemplified embodiment the fibers are discharged or
flashed into vaporization vessel 8 which is at atmospheric pressure
and substantially all of the solvent vaporizes and passes out
through conduit 9 leaving the fibers dispersed in the water. The
water intimately contacts the surfaces of the fibers and
advantageously prevents fusing or sticking together of the fibers
so that they remain dissociated in a loose mass. The fibers thus
remain in discrete form as contrasted to the tangled and fused
product which results from prior art melt spinning or solvent
spinning (e.g., plexifilaments) of the prior art.
The water not only has the ability to favorably affect the
resulting product as just mentioned but it provides additional
benefits as well. It is believed that during discharge of the
dispersion the water assists in crystal orientation and fiber
development during and prior to precipitation of the polymer. This
occurs possibly by the separation of the dissolved polymer into
individual drops or globules which may more readily permit
formation of separate, independent fibers when they are subjected
to shear stress. The use of water, because of its high density in
comparison with most solvents, may also enhance the turbulence and
shear forces acting on the drops of dissolved polymer during
discharge, thereby enchancing orientation and fiber formation.
Additionally, the sensible heat energy or enthalpy of the water at
the elevated temperatures of operation is available to assist in
the evaporation of the solvent during discharge. Therefore the
water, which has high enthalpy, permits the use of lower
temperatures prior to discharge or flashing while still effecting
vaporization of substantially all of the solvent upon discharge.
The ability to use lower pressures provides the corresponding
ability to use lower pressures prior to discharge with the
attendent economies of lower pressure operation. Also, the water
lowers the temperature of the fibers after flashing due to the
phenomenon of the water-solvent mixture having a lower boiling
point than the solvent or water alone.
The lower the ratio of solvent to water employed, the more
pronounced is this effect and even lower temperatures of operation
may be possible. Lower solvent to water ratios are therefore
preferred, e.g., below 1 : 1 for polyethylene, where this is
consistent with other variables affecting the fiber properties
desired. Also, the water has a "steam stripping" type of effect
during vaporization of the solvent which tends to decrease the
temperature of the fiber mass during flashing so that it may more
readily be decreased below the softening point of the polymer.
One of the most important variables in controlling the fiber length
is the ratio of solvent to water. For a given polymer and polymer
solution concentration, the higher the ratio of solvent to water,
the longer are the fibers that result. The lower such ratio is, the
shorter are the fibers.
The viscosity of the polymer solution is another variable affecting
fiber length and this is related to the nature of the polymer and
its concentration in the solvent. The higher the molecular weight
and the higher the polymer concentration in the solvent of the
polymer, the longer the resulting fibers. Polymers that crystallize
more rapidly, such as polyethylene, tend to produce shorter fibers
under similar conditions of viscosity. In fact, for polypropylene
under most operating conditions for rpoducing fibers of desirable
properties, the fibrous product from flashing is a substantially
continuous complex of fibrous material. On the other hand,
polyethylene produced under similar conditions results in much
shorter fibers.
Also, the higher the shear forces during discharge the longer the
fibers that result. Therefore the factors controlling shear force,
i.e., the pressure gradient, temperature of operation, the size and
configuration of the discharge conduit and nozzle, may also be
adjusted as previously discussed to assist in fiber length
control.
The fibers, dispersed in the water after flashing from the zone of
reduced pressure, may be dried to a lower moisture content and used
without further treatment for uses not requiring carefully
controlled fiber length. Such uses include molding pulp use, use as
non-wovens, as an absorption or insulation material or the
like.
It is particularly advantageous for manufacture of a paper pulp
under this invention to adjust operating conditions to produce a
pulp having a fiber length somewhat longer than the actual fiber
length desired, for example average length of 5 to 10 mm or even up
to 100 mm or longer. This product can then be beaten or cut to the
exact fiber length and fiber length distribution to correspond to
natural cellulose pulp or to such other length as may be desired.
In this manner the properties of the final product can be more
exactly controlled. In some cases, as with polypropylene, it may be
desirable even to produce a fiber product of continuous nature and
beat or cut this product to a length resembling cellulose fiber
length in order to provide the strongest fibers. In such instances
it is most important to carry out the refining operation upon the
fibrous product immediately after flashing and while it is still at
an elevated temperature, preferably above 50.degree.C, initially,
and usually around 60.degree.-70.degree., initially. This is
because once the material has cooled it is impractically difficult
to refine or cut because it becomes tough and fused together. The
initial refining may be followed by additional refining at room
temperature.
The invention will be illustrated by specific embodiments set forth
in the following examples, but the scope of the invention to be
protected is not limited thereto.
EXAMPLE 1
To a SUS-made 5 liter autoclave of the general type depicted in
FIG. 1, equipped with a stirrer and a jacekt through which steam at
10 kg/cm.sup.2 is introduced to heat the autoclave was added with
stirring to dissolve the polymer prior to addition of the water and
water dispersing agent.
______________________________________ polyethylene (molecular
weight 28,000 and melt index 14). (Trade name: HiZex 1300J) 100
grams water 2 liters n-hexane 1 liter polyvinyl alcohol, (degree of
saponifi- cation 86.5-89 mol %, degree of poly- merization above
1500 and viscosity at 4% water solution of 20.degree.C is 30
centipoise). (Trade name: GH-17) 2.5 grams non-ionic surfactant
(alkyl phenol ethylene ether). (Trade name: Nissan Nonion NS 210) 3
grams ______________________________________
The mixture was stirred and heated to 140.degree.C after the
atmosphere within the system was replaced with nitrogen.
Polyethylene was dissolved completely by maintaining the above
temperature for 30 minutes. The viscosity of the solution was 100
centipoises. Thereafter, water, PVA, and surfactant were introduced
and the mixture was kept at this temperature for 30 minutes
resulting in a homogenous suspension. This suspension was flashed
to the atmospheric pressure through conduit 4, a copper pipe, and
cock valve 5. However, no nozzle, such as nozzle 6 was employed.
Flashing was continued for about 15 seconds until the pressure
inside the autoclave dropped from 11 kg/cm.sup.2 -g to 1
kg/cm.sup.2 -g. The resulting polymer fibrous materials were
separated from vaporous n-hexane in the vaporization vessel. The
pressure inside the vaporization vessel was maintained at the
atmospheric pressure and its temperature was 80.degree.C at the end
of the flashing. The polymer fibrous materials thus produced
contained residual hexane of less than 0.5 percent and was refined
for 15 minutes by a Waring blender, resulting in beaten pulp. This
pulp fiber showed a strength of 3 g./d.
COMPARATIVE EXAMPLE 1
To the same apparatus as used in Example 1, were added only
polyethylene (Trade name: Hi-Zex 1300J) 105 grams and n-hexane 3
liters
The content was stirred and the atmosphere inside the system was
replaced with nitrogen followed by heating at 140.degree.C. The
viscosity of the solution was less than 100 centipoises. After
maintaining at the same temperature for 30 minutes, the content was
transferred by being flashed to the atmospheric pressure into a 10
liter autoclave through conduit 4 and cock valve 5 (but without
nozzle 6). Hexane was then filtered out by centrifugal separation
and the polymer was washed with four portions of 1 liter acetone,
then with four portions of 1 liter water and centrifuged, resulting
in an aqueous slurry substantially free of hexane. It was then
beaten for 15 minutes by the Waring blender, resulting in beaten
pulp. This synthetic pulp had the strength of only 0.6 g./d and was
incapable of being hand-sheeted as it was.
EXAMPLE 2
______________________________________ polypropylene (molecular
weight 240,000, melt index 12.0 isotacticity index 96.5 and
intrinsic viscosity = 1.9) (Trade name : Mitsui Sekiyu Kagaku,
Polypro F 707) 100 grams Water 2 liters n-hexane 1 liter polyvinyl
alcohol (Trade name: Gosenol GH - 17) 2.5 grams and non-ionic
surfactant (Trade name: Nissan Nonion NS 210) 3 grams
______________________________________
were processed as in Example 1 except that nozzle 6 was employed,
and flashed at 140.degree.C resulting polymer fibrous material was
refined for 15 minutes by the Waring blender. The synthetic pulp
revealed a strength of 2.5 g./d.
COMPARATIVE EXAMPLE 2
Polypropylene (Trade Name: Misui Sekiyu Kagaku Polypro F 707) 30
grams and n-hexane 3 liters
were treated as in Comparative Example 1, flashed, centrifuged and
the hexane slurry was replaced with water slurry according to the
procedure of Comparative Example 1. After refined for 15 minutes by
the Waring blender, a synthetic pulp was obtained. The resulting
pulp was fragile like glass fibers having a strength of only 0.2
g./d. and unable to be hand-sheeted as it is.
EXAMPLE 3
______________________________________ 4-methyl-1-pentene
homopolymer (isotacticity index in heptane 98.6, .eta. = 12) 100
grams water 1 liter benzene 2 liters polyvinyl alcohol (Trade name:
Gosenol GH-17) 2.5 liters and non-ionic surfactant (Trade name:
Nissan Nonion NS 210) 2.5 grams
______________________________________
were processed as in Example 1 and flashed at 140.degree.C. The
resulting polymer fibrous materials were refined for 5 minutes by
the Waring blender. The resulting product revealed a strength of
1.0 g./d.
EXAMPLE 4
______________________________________ Polypropylene (Trade name:
Mitsui Kagaku Polypro F 707) 70 grams polystyrene (Trade name:
Styron 666) 30 grams and hexane 1 liter.
______________________________________
were heated to and maintained at 150.degree.C for 30 minutes to
dissolve. Then 3 grams of a surfactant (Trade name: Nissan Nonion
NS 210) and 2.5 grams of polyvinyl alcohol (Trade name : Gosenol
GH-17) dissolved in 2 liters of water were introduced to the
solution with pressure and stirred for 30 minutes to obtain a
suspension which is then flashed to the atmospheric pressure. The
resulting fibrous material was refined for 10 minutes by the Waring
blender to produce synthetic pulp. The pulp showed a strength of
2.5 g./d.
EXAMPLE 5
______________________________________ Polyethylene (Trade name:
HiZex 1300J) 100 grams water 2 liters n-hexane 1 liter and
polyvinyl alcohol (Trade name : Gosenol GH-17) 1 gram
______________________________________
were treated as in Example 1 and flashed at 140.degree.C. The
viscosity of the solution was about 100 centipoises at
140.degree.C. The resulting fibrous material formed a collection of
fibers slightly harder than the product of Example 1. After
refining for 30 minutes by the Waring blender, it showed a strength
of 2.1 g./d.
EXAMPLE 6
Polyethylene (Trade name: HiZex 1300 J) 100 grams water 2 liters
n-hexane 1 liter and gelatine (animal gelatin from Nitta gelatin) 3
grams
were treated as in Example 1 and flashed at 140.degree.C. The
viscosity of the solution was about 100 centipoise at 140.degree.C.
The resulting fibrous material was refined by the Waring blender.
The resulting fibers showed a strength of 3.0 g./d.
EXAMPLE 7
Polyethylene (Trade name: Hi-Zex 1300 J) 70 grams Calcium carbonate
powder (Trade name: Homocal-D) 30 grams n-hexane 1 liter water 2
liters Polyvinyl alcohol (Trade name: Gosenol GH-17) 2.5 grams
non-ionic surfactant (Trade name: Nissan Nonion NS 210) 3 grams
were treated as in Example 1 and flashed at 140.degree.C. The
viscosity of the solution was about 100 centipoises at
140.degree.C. The fibrous material thus obtained was refined by the
Waring blender, resulting in synthetic pulp containing about 27
percent by weight of calcium carbonate. The pulp revealed a stength
of 1.0 g./d. This example illustrates that modifying agents such as
pigment may be added to the dispersion to alter the character of
the resulting fibers.
COMPARATIVE EXAMPLE 3
______________________________________ Polyethylene (Trade name:
Hi-Zex 1300 J) 100 grams water, and 2 liters n-hexane 1 liter
______________________________________
were processed as in Example 1 and flashed at 140.degree.C. through
a cock valve with an opening diameter of 6 mm as shown at 13 in
FIG. 1 but without nozzle 14. After flashing was completed, the
autoclave was checked to find the side wall of the autoclave and
the stirrer were covered by hard polyethylene adhered to the
surfaces. The resulting fibrous materials were refined in the
Waring blender for 30 minutes but the product contained many
particles and the product was not practical for use as a synthetic
pulp. This example illustrates the production of fibers without use
of water dispersing agent prior to flashing.
EXAMPLE 8
Polyethylene (120,000 mol.weight) 50 grams n-hexane 1 liter water 2
liters polyvinyl alcohol (Gosenol GH-17) 0.5 grams
To the 5 liter autoclave as depicted in FIG. 1 the polyethylene and
n-hexane were added with stirring and heat to dissolve the polymer.
The viscosity of this solution at 140.degree.C was 200 centipoise.
Water containing PVA was then added and the system flushed with
nitrogen. These materials were heated with stirring for 30 minutes
to form a uniform dispersion at a temperature of 140.degree.C. The
dispersion was then discharged through conduit 4 and flash nozzle
6. Conduit 4 had an internal diameter of 7 mm and a length of
approximately 6 meters and nozzle 6 had a diameter of 3 mm and a
length of 21 mm.
The fibers were collected without refining and inspected. These
fibers had an average length greater than 100 mm and some were
substantially continuous. They constituted very strong small hollow
tubes having average diameters ranging from 30 to 180 and the walls
of the tubes were composed of a thin film having an average
thickness less than 2.
EXAMPLE 9
Example 8 was repeated utilizing 70 grams of the polyethylene
instead of 50 grams. The viscosity of the solution of polymer in
the hexane was 400 centipoises at 140.degree.C. The structural
character and dimensions of the fibers were substantially the same
except the fibers produced were longer and stronger. These fibers
are particularly suitable for use in manufacture of non-wovens and
the like or they can be refined to be used as a cellulose pulp
substitute.
EXAMPLE 10
Polyethylene fibers were prepared utilizing the procedures of
Example 1, by flashing through a cock valve 6 mm in diameter as
shown at 13 in FIG. 1 but without nozzle 14. Also, the fibers were
refined in a Beloit single disc refiner having 12 inch discs,
rather than in a Waring blender.
The resulting fibers were tested for various drainage resistance
characteristics in accordance with the procedures described in
TAPPI 37, No. 11 : pp. 523-534. They were also tested for drainage
time and drainage factor in accordance with the procedure described
previously. The results are as follows:
Sample Mv .times. S V M N DT DF 10.sup..sup.-3
______________________________________ 1 65 1.54 2.93 .00296 .340
8.0 1.0 2 28 1.17 2.65 .00434 .309 6.2 -- 3 41 1.26 2.16 .00434
.309 7.1 1.1 where M.sub.v = viscosity average molecular weight S =
hydrodynamic specific surface area m.sup.2 /g V = hydrodynamic
volume, cc/g M & N = compressibility constants DT = drainage
time, seconds DF = drainage factor, seconds/g Process Conditions
Sample Mv Concentration Hexane/Water PVA/ Hexane Vol/Vol Polymer
______________________________________ 1 65,000 50 1/1 1 2 23,000
100 1/2 1 3 41,000 75 1/2 1 Refining Conditions Sample Number of
Passes Number of Passes Temperature With Refiner Disk With Refiner
Disk Clearance at Clearance at 10 0 Micron. Micron
______________________________________ 1 8 4 65 - 70.degree.C 2 4 5
70 - 80.degree.C 3 8 5 60.degree.C
______________________________________
COMPARATIVE EXAMPLE 4
Polyethylene fibers prepared in accordance with the process
described in U.S. patent application Ser. No. 257,609 were tested
as in Example 10. The results are as follows:
Drainage Resistence Characteristics
______________________________________ Sample Mv .times.
10.sup..sup.-3 S V M N DT DF ______________________________________
1 100 0.88 1.95 .0072 .266 5.5 0.78 2 100 0.83 1.88 .00695 .270 --
-- 3 65 0.70 1.83 .0101 .245 5.1 -- 4 300 0.93 2.03 .00635 .274 5.7
0.89 5 44 0.81 2.24 .0124 .218 5.3 0.65
______________________________________
It is seen that the fibers prepared in accordance with the present
invention have a more favorable hydrodynamic surface area,
compressibility constant N and drainage time.
EXAMPLE 11
Polypropylene powder (molecular weight 160,000, melt index 55,
intrinsic viscosity 1.5 and isotactivity index 94.7) is utilized in
this example together with 1% PVA based on the polypropylene. The
PVA used was supplied from Nippon Gosei (Grade NCO 5) and had a
viscosity of 4 percent in water at 20.degree.C of 5.3-0.7, a degree
of saponification of 98.5-100 percent and a degree of
polymerization of under 1000. The polymer was dissolved with
n-hexane in the autoclave of FIG. 1 and then the PVA and water were
added and the autoclave purged with nitrogen. The mixture was
agitated for 30 minutes to form and heat the dispersion to
160.degree.C with a pressure of 15 kg/cm.sup.2 . The dispersion was
then discharged to atmospheric pressure through conduit 4 and
nozzle having the dimensions described in Example 8 into
vaporization vessel 8 which was at atmospheric pressure and
contained nitrogen gas.
The continuous fibrous product was immediately refined at 10,500
rpm for 20 minutes in a Waring blender with a beginning temperature
of approximately 10.degree.C and a temperature at the end of
refining of about 40.degree.C with a concentration in the blender
of 10 grams fiber in 1 liter water. A number of runs were made
using a progression of hexane/water ratios of 5/10, 7.5/10 and
10/10 on a volume basis. For each indicated ratio of runs were made
with the following series of polymer concentrations 25, 50, 75, 100
and 200 grams/liter of solvent.
The handsheet properties of the refined product were tested and the
results are shown in following Tables I and II. Also the influence
of the temperature of beating was studied and is shown in Table
III.
Table I
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Properties of Handsheet
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Hexane/Water Basis = 5/10 Weight Caliper Apparent Opacity Tear g/
Zero Span Tensile Test gm/m.sup.2 10.sup..sup.-3 mm Density % Sheet
Km lb/in %
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25.sup.G/L-C6 62.8 418 0.150 97.2 3 0.22 0.07 1.6 50 50.7 312 0.162
95.3 5 0.31 0.19 2.5 75 60.4 346 0.174 97.3 5 0.30 0.21 2.8 100
59.5 357 0.166 96.3 11 0.39 0.62 3.1 200 60.9 301 0.202 97.0 11
1.10 1.0 2.7 Hexane/Water = 7.5/10 (At 25 G/L-C6 100% SWP handsheet
could not be obtained) 50 60.0 386 0.155 95.9 2 0.38 0.15 2.2 75
55.7 336 0.165 95.8 3 0.55 0.23 3.0 100 59.2 330 0.179 96.6 3 0.77
0.44 2.4 Hexane/Water = 10/10 25.sup.G/L-C6 100% SWP handsheet
could not be obtained 50 73.2 468 0.158 94.1 1 0.31 0.06 2.0 75
61.7 367 0.168 95.9 3 0.44 0.20 2.3 100 60.2 306 0.196 95.9 3 0.62
0.43 2.2
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Note: .sup.G/L-C6 =grams polypropylene/liter hexane
Table II ______________________________________ Freeness
______________________________________ Polypropylene grams/liter
5/10 7.5/10 10/10 15/10 ______________________________________ 25
426 559 -- -- 50 416 497 520 566 75 -- 483 -- -- 100 350 417 373 --
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Basis Weight Caliper Apparent Opacity Tear g/ Zero g/m.sup.2
10.sup..sup.-3 mm Density % Sheet span Tensile Test g/cc Km Lb/in %
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(start of refining) ( -end of refining) (16-41.degree.C) 60.5 246
0.245 96.1 8 1.01 0.70 1.6 (16-41.degree.C) 60.5 260 0.232 96.7 14
1.07 0.45 0.8 (60-70.degree.C) 57.5 258 0.222 95.6 1 1.03 0.24 0.8
(74-78.degree.C) 54.7 234 0.233 94.8 1 1.03 0.14 0.6
(11-43.degree.C) 52.3 262 0.199 96.0 5 1.03 1.1 4.6
(63-66.degree.C) 49.6 277 0.179 95.2 2 0.83 0.37 1.5
(77-78.degree.C) 46.8 260 0.180 95.0 2 0.85 0.13 0.6
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Note: Higher temperature of refining always gives longer
fibers.
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