U.S. patent number 3,891,499 [Application Number 05/257,609] was granted by the patent office on 1975-06-24 for synthetic papermaking pulp and process of manufacture.
This patent grant is currently assigned to Crown Zellerbach International, Inc.. Invention is credited to Teiji Kato, Katsumi Okamoto.
United States Patent |
3,891,499 |
Kato , et al. |
June 24, 1975 |
Synthetic papermaking pulp and process of manufacture
Abstract
A pulp of synthetic polymer fibers useful for papermaking. The
fibers have the appearance of rolled or folded sheets at a
magnification of about 500X and are distinct from one another,
being only mechanically intertwined. The fibers are of papermaking
size, no more than about 10 percent by weight of the fibers being
retained on a 20 mesh screen but at least about 25 percent by
weight are retained on a 65 mesh screen. The pulp has a drainage
factor greater than about 0.2 seconds/gram and a compressibility
constant N greater than about 0.2. The pulp is preferably formed of
high molecular weight polyethylene or polypropylene. Also, a
process for forming polymer fibers comprising forming a solution of
a crystalline polymer in a solvent at a temperature above the melt
dissolution temperature of the polymer, passing the polymer
solution through a precipitation zone into a region of reduced
pressure whereby a portion only of the solvent is adiabatically
vaporized and the polymer is precipitated as a highly swollen
fibrous mass or gel, separating the solvent vapor from the gel, and
subjecting the fibrous gel to attritional forces to liberate the
individual, discrete polyolefin fibers therefrom.
Inventors: |
Kato; Teiji (Iwakuni,
JA), Okamoto; Katsumi (Kodaira, JA) |
Assignee: |
Crown Zellerbach International,
Inc. (San Francisco, CA)
|
Family
ID: |
26377473 |
Appl.
No.: |
05/257,609 |
Filed: |
May 30, 1972 |
Foreign Application Priority Data
|
|
|
|
|
Jun 3, 1971 [JA] |
|
|
46-38260 |
Dec 28, 1971 [JA] |
|
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46-105654 |
|
Current U.S.
Class: |
162/157.5;
264/13; 264/205 |
Current CPC
Class: |
D21H
5/202 (20130101); D01D 5/11 (20130101); C08F
10/00 (20130101); D21H 13/14 (20130101); C08F
10/00 (20130101); C08F 2/38 (20130101) |
Current International
Class: |
D01D
5/00 (20060101); D01D 5/11 (20060101); C08F
10/00 (20060101); D21F 011/00 () |
Field of
Search: |
;162/157C,157R,146
;264/5,13,14,121,205 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Bashore; S. Leon
Assistant Examiner: Chin; Peter
Attorney, Agent or Firm: Horton; Corwin R. Teigland; Stanley
M. Howard; Robert E.
Claims
We claim:
1. A process for forming a synthetic pulp of discrete polyolefin
fibers comprising forming a solution of a crystalline polyolefin
selected from the group consisting of polyethylene, polypropylene
and copolymers of ethylene and propylene in a solvent the
polyolefin being present in an amount between about 0.5 and 5
percent by weight of the solution, the solution being formed at
autogeneous or higher pressure at a temperature above the melt
dissolution temperature and at a temperature which will cause
between about 20 percent and about 70 percent by weight of the
solvent to vaporize upon adiabatic flashing into a zone of reduced
pressure, rapidly passing the solution into said zone of reduced
pressure to vaporize a portion only of said solvent and precipitate
a fibrous polyolefin gel containing less than about 7 percent by
weight of the polyolefin, and passing the fibrous polyolefin gel
through a disc refiner to liberate discrete polyolefin fibers.
Description
BACKGROUND OF THE INVENTION
This invention relates to a synthetic pulp for making paper and
similar products. The invention provides a novel pulp of olefin
polymers, and provides also a method of making a synthetic
paper-making pulp from an olefin polymer.
Paper is traditionally made from a pulp of cellulose fibers
(primarily wood fibers); in idealised form a cellulose fibre in
papermaking pulp comprises a longitudinally extending body of
roughly circular cross-section, having a length typically in the
range 0.1 mm. to 4.0 mm. and an average diameter typically in the
range 0.01-0.05 mm. from which body project fine hair-like
"fibrils"; the body of the fibre is thought to be made of tightly
wound fibrils, some of which are caused to project in the course of
pulp preparation.
There have been many prior attempts to use synthetic polymers as a
substitute for wood in papermaking. Among the earliest is the use
of conventional staple fibres. Polymer staple is the product
obtained by making a filament of the polymer (either by extruding a
melt of the polymer through an orifice so that it cools as a
continuous solid filament or by extruding a solution of the polymer
into an atmosphere hot enough to evaporate the solvent and leave a
continuous filament) and chopping the filament into pieces of the
desired length. Staple fibres are produced for use mainly as
textile fibres, and do not make good paper; staple fibres are
essentially smooth-surfaced cylinders.
There have been proposals to make synthetic fibres having a
structure more elaborate than the structure of staple, and some of
these structures appear to give a better paper than staple.
For example, the so-called "plexifilaments" described in British
Patent Specification No. 891,943 and German Patent Specification
No. 1,292,301 are made up of very thin (less than 2 .mu.) film or
ribbon-like structural units which are interconnected to form a
unitary three-dimensional network; this filamentary structure
comprises a plexus composed of film-like or ribbon-like elements
which unite and separate at random intervals.
Another structure of fibres for paper-making is disclosed in German
laid-open Specification No. 21 21 512. This is described as
consisting of interior fibrils which converge, while the number of
outside fibrils is small; this is alternatively described as a
bundle of fibrils, bands or threads.
Both plexifilaments and the fibres of German Specification No. 21
21 512 are made by flash evaporation of a heated, pressurised
liquid containing dissolved polymer; in the case of plexifilaments
a hot solution under pressure is expanded through a nozzle into a
lower pressure zone so that all the solvent flashes off to cause
bubble nucleation, while according to German Specification No. 21
21 512 a hot aqueous emulsion containing a polymer solution as
disperse phase is similarly flashed to evaporate the solvent.
The polymer precipitated from its solution on flash evaporation of
the solvent appears to be basically in thin sheet form in both the
foregoing procedures.
Other processes of flash evaporation of solvent from a solution of
polymer have been described in German Patent Specifications Nos.
1,958,609 and 1,951,609; though the products of those processes
have been less clearly described, they also appear to have a sheet
as their basic unit. The product of German Specification No.
1,958,609 appears to consist of micro-flakes which are loosely
aggregated, so that the micro-flakes can be de-aggregated in an
organic solvent, whereby there is obtained a suspension of flakes
in solvent which suspension is made into paper. The product of
German Specification No. 1,958,609 contains fibre-like elements
which are fused at their ends, like plexifilaments.
None of the foregoing products is commercially satisfactory as a
paper-making material in substitution for wood-pulp. The object of
this invention is to provide a polymeric substitute for wood-pulp,
and we have achieved this by directing attention to not only the
individual fibre structure, but the collection of fibres as a
whole.
DETAILED DESCRIPTION OF THE INVENTION
We have invented a pulp useful for papermaking based on sheets of
the polymersuch as are formed by flash evaporation of a solution of
the polymer, which makes very good paper. In our pulp, the fibers
are rolled or folded thin films or sheets which are in the form of
rolls or tubes, and these rolls or tubes are distinct from each
other so that instead of extending in bunches in the same general
longitudinal direction, they extend in random directions relative
to each other and are mechanically intertwined rather than bonded
together at crossover points and can be separated from one another
by pulling apart. This random orientation of longitudinally
extending rolls of polymer sheet or fibers is seen best at a
magnification of 500X or 1000X, and to facilitate appreciation of
this structure which we find to give uniquely satisfactory
properties we refer to FIGS. 4 to 7 of the accompanying drawings
which are electron micrographs at 500X and 10,000X of the products
obtained respectively in Example 1 and in Example 3 run 5 of the
following description.
In FIG. 4 there can be seen in the foreground a number of rolls
extending from side to side of the picture, not joined to each
other, and behind them other distinct rolls which extend from top
to bottom. The ends of some of these rolls are clearly visible.
Similarly in FIG. 6 there can be seen rolls of polyolefin film, the
ends of some of the rolls being visible, and as in FIG. 4 the
significant feature of these rolls is that, while each has its own
longitudinal direction, the longitudinal directions of the rolls
are criss-cross.
The fibers, or rolls of polymer sheet, may be convoluted or
intertwined in the pulp of our invention, but the fact of being
convoluted indicates that they are distinct fibers or rolls. (By
"convoluted", we mean that one fiber or roll and another are wound
longitudinally as loose helices around each other).
Thus the present invention provides a synthetic pulp for
paper-making comprising a polymer in the form of thin films
produced by flash evaporation of solvent from a solution of the
polymer, characterised in that the thin film is in the form of
longitudinally extending rolls which are distinct from one another,
the longitudinal directions of adjacent rolls being different from
each other.
In our pulp, it is preferred that the surfaces of a large number of
the separate rolls in any given sample of pulp exhibit a
"shark-skin" texture. A shark-skin texture is a succession of
wrinkles or corrugations parallel to each other and transverse to
the longitudinal direction of the roll. A pulp containing few
fibers or rolls with little or no shark-skin texture can be a good
pulp for paper-making, but we find that a pulp wherein there are
many shark-skin-surfaced fibrous elements is particularly good. We
prefer a special form of shark-skin surface in which there are
grooves or valleys which extend in the direction of the roll and
wrinkles which extend, transversely of the roll, between the
grooves. The shark-skin texture may however degenerate to a pebbled
texture; both shark-skin surface and pebbled surface appear to
contribute to the valuable properties of the fibres and are a
preferred secondary characteristic of our pulp. The preferred
shark-skin surface is shown in FIGS. 5 and 7, which shows the
central area of the micrographs of FIGS. 4 and 6 respectively at
twenty times greater magnification, i.e, at 10,000X.
The thin sheet or film of the fiber or roll can be at least
partially unrolled by an ultrasonic probe, and has an uneven
thickness that is generally between about 1 and 10 microns.
Thus the pulp of this invention can be recognised by its "course"
morphology of separate, randomly oriented rolls of thin film which
is visible at a magnification of 500X, and its "fine" morphology of
a shark-skin surface visible at a magnification of 10,000X.
A majority (by weight) of the fibers that may be produced in
accordance with this invention for use in papermaking have average
lengths (as measured by TAPPI Test T232 SU68) between about 0.3 mm.
and 10 mm. and preferably between about 1.0 mm. and 5.0 mm. If the
fibers are longer than about 5.0 mm., the danger of flocculation
during papermaking increases. Stated another way, 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 are retained on a 35 mesh screen.
A majority (by weight) of the fibers that may be produced in
accordance with this invention have a diameter between about 0.01
mm., 0.10 mm. and preferably between about 0.01 mm. and 0.03
mm.
Since the diameter of individual fibers varies along the length
thereof, it is sometimes more convenient to characterize the
slenderness of the fibers by reference to their coarseness.
A majority (by weight) of the fibers of the present invention have
an average coarseness (as measured by TAPPI Test T234 SU67) between
about 1 and 5 decigrex (mg/100m) and typically between about 3.5
and 5 decigrex. Fibers having a coarseness larger than about 5
decigrex have increasingly poor drainage characteristics which
makes them less suitable for papermaking.
The gas adsorption surface area of the fibers of the present
invention is greater than 1.0 m.sup.2 /gram. Typically, the gas
adsorption surface area will range as high as about 30 m.sup.2
/gram for steam stripped or solvent exchanged (through isopropanol
to water from the solution solvent) fibers and as high as 200
m.sup.2 /gram for fibers freeze dried from the solution
solvent.
The hydrodynamic surface area of the fibers of the present
invention is greater than about 0.6 m.sup.2 /gram and typically
will range between about 0.6 and 1.0 m.sup.2 /gram. This latter
characteristic is more closely related to the drainage
characteristics of fibers to be used in papermaking from an aqueous
slurry than is the gas adsorption surface area.
Determination of hydrodynamic specific surface area is made 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" surface area (S) discussed herein.
Since it is difficult and time consuming to measure the
hydrodynamic surface area of fibers, their drainage characteristics
can be more easily characterized by drainage time. The drainage
time of the fibers produced by the present process is greater than
about 5 seconds and typically between about 5 and 6 seconds.
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 T205 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 mole 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.
A more accurate characterization of drainage characteristics, 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 0.2 preferably greater than 0.5 and typically
ranges up to 1.0 seconds/gram. This characteristic 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.
A further measure of the drainage characteristics of fibers is the
compressibility 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 by Ingmanson
etal.
The compressibility constant N of cellulosic fibers is typically
between 0.3 and 0.4. The compressibility constant (N) of the
present fibers is greater than about 0.2 and typically between
about 0.2 and 0.3.
The values given above for the various drainage characteristics,
i.e., hydrodynamic surface area, drainage time, drainage factor and
compressibility constant were all determined on fibers treated with
2 percent by weight polyvinyl alcohol but similar values would be
expected with other water dispersing agents.
According to the present invention, there is provided a process of
making polymer pulp suitable for making paper. The process of this
invention, like the prior art processes discussed above, depends on
flash-evaporation of solvent from a solution of the polymer. But
our process calls for particular evaporation conditions followed by
a further attritional treatment (refining) step which produces a
pulp containing discrete fibrous elements of optimum
properties.
In our process, a solution of polymer, at temperature sufficient to
cause the polymer to dissolve in the solvent and at a pressure at
least sufficient to keep the solvent in liquid phase at said
temperature, is subjected to reduction in pressure such that part
but not all of the solvent evaporates so that the polymer
precipitates from solution as a highly swollen fibrous mass or
fibrous gel. Thus there is formed a fibrous structure containing
interconnecting capilary spaces filled with solvent. The gel should
be of low enough polymer concentration to permit liberation or
separation of discrete fibers by attritional forces preferably
imparted by mechanical refining. After refining the fibers have the
structure described above. By refining, we mean that mechanical
treatment of pulp which in the paper-making industry is termed
refining. The favoured instrument for refining is a disc-refiner,
so in its preferred form the refining step in the process of this
invention comprises passing the gel of polymer in solvent
continuously through a refining space defined by mutually opposed,
relatively rotating, surfaces.
Disc refiners are of two main types, "single-disc" refiners which
have two coaxial discs of which one is stationary while the other
rotates on the axis at a short axial spacing from the stationary
disc, and "double-disc" refiners which have two coaxial discs which
both rotate, in opposite senses of rotation, on the axis at a short
axial spacing from each other.
Disc refiners are constructed so that the clearance between the
discs can be varied, and for the refining step of our process which
follows the production of a refinable gel, we prefer a clearance of
between about 100 to 125 microns for the initial fiber liberation.
Additional, or secondary refining of the fibers is preferably
accomplished at a clearance of between about 25 and 75 microns.
A disc refiner is the preferred refining or beating apparatus for
imparting attritional forces to the fibrous gel to liberate or
separate discrete fibers; however, an alternative but less
preferred refining apparatus is a "beater", generally known in the
paper industry, as a Jordan.
Thus, in general, refining the fibrous gel consists of subjecting
the gel to attritional forces in a space defined by surfaces moving
relative to each other in close proximity.
In the flash evaporation of a solution, there are many operating
parameters which can affect the nature of the product, and in the
first, flash evaporation, step of our process these are controlled
primarily to give only partial evaporation, so that at most 60
percent or perhaps 70 percent of the solvent evaporates (preferably
at least 20 percent of the solvent evaporates) and a refinable gel
is formed.
These parameters are:
Concentration of the solution.
A relatively dilute solution. is preferred, especially a solution
containing less than 5 percent by weight of polymer. Such dilution
is especially important in the case of high molecular weight
polyolefins (as discussed below) in order to permit ease of
handling, since a concentrated solution of high molecular weight
polyolefin can have a viscosity at the solution temperature in
excess of 500 cp. Even with low molecular weight polymers, however,
it is also advantageous to keep the polymer concentration below 5
percent by weight, to ensure formation of a fibrous gel having the
preferred polymer concentration. A polymer concentration in the
range 10-20 percent may be used for lower molecular weight
polymers; however this presents difficulties which will be
discussed further below.
Temperature of the solution.
The solvent must of course be hot enough to cause the polymer to
dissolve, i.e. above the melt dissolution temperature which depends
on the solvent. Types of solvent and determination of melt
dissolution temperature are discussed below. Moreover, the
temperature of the solution must not be so high that the sensible
heat of the solution is sufficient to evaporate more than about 70
percent of the solvent when the pressure on the solution is
relieved; determination of the sensible heat is also discussed
below.
Pressure on the solution.
The pressure of the solution immediately before flash evaporation
is in general at least the autogeneous pressure of the solution at
the given temperature, in order to have the solvent in liquid phase
up to the time of evaporation. A pressure higher than the
autogeneous pressure can be established by use of an inert gas in
the vapor space of the solution vessel or by pumps as described
below with reference to the drawings. Furthermore a small
proportion of solvent may be present as vapour even before the
adiabatic expansion, as this seems to cause "vapor cutting". By
vapor cutting, we mean that the bubbles of vapor cut the fibrous
gel noodles to more suitable lengths.
Pressure and viscosity determine speed of flow, which in turn
affects shear as discussed below.
Pressure drop on evaporation.
Normally the flash evaporation is effected by discharging the
pressurised solution into a zone at substantially atmospheric
pressure, although slightly super-atmospheric or sub-atmospheric
pressures may be employed. Simple thermodynamic calculations will
determine the appropriate temperature of the solution to cause a
predetermined evaporation of solvent boiling at a given
pressure.
The expansion of the solution into the lower pressure zone is an
adiabatic expansion wherein the heat for evaporation of the solvent
is taken from the body of solution, as opposed to evaporation for
which the heat is supplied from outside. It is not necessary to
ensure strictly adiabatic conditions, by insulating the apparatus
to prevent all heat-exchange with the environment.
Flow-rate.
The simplest and most practical way to cause sudden evaporation of
part of the solvent -- with consequent reduction in temperature of
the solution and precipitation of polymer -- is to pass the
solution continuously through an adiabatic expansion nozzle. The
size of the nozzle, together with the viscosity of the solution
(which in turn is concentration and temperature dependent)
determines the speed of flow which generally should exceed 10
meters per second and preferably is in the range 50-150 meters per
second. The speed of flow should be sufficient to cause turbulence
on exiting from the nozzle. Flow which is unstable but below the
velocity needed for melt fracture (elastic turbulence) can produce
the desirable shark-skin effect.
Desirably the flow rate is in the range 60-127 m./sec., and a flow
rate of 70-90 m./sec. is found commercially useful.
The operating parameters will be selected on the principles
outlined above to give fibres of the described characteristics,
having regard to the polymer and to the solvent used.
Any crystallizable polymer may be used in accordance with the
present invention to form a synthetic pulp provided that a suitable
solvent may be found to dissolve the polymer. In particular
crystallizable addition polymers, especially crystallizable
polyolefins are useful. Particularly preferred are crystalline
polyethylene, crystalline or predominantly crystalline (isotactic)
polypropylene and crystalline ethylenepropylene copolymers.
Additionally, polybutenes, polymethyl pentenes and polystyrene may
be desirable polymers in the practice of this invention.
Crystalline poly-amides and polyesters may be used.
The preferred crystalline polyolefin homopolymers or copolymers for
papermaking purposes that may be employed are those of high
molecular weight. By "high" molecular weight is meant a polyolefin
having a melt index (as determined by ASTM Standard Test No. D-
1238) of less than 0.5 and preferably essentially zero. A zero melt
index for high density polyethylene corresponds to a viscosity
average molecular weight greater than about 100,000 (n = 3.0), and
a zero melt index (or melt flow) for substantially isotactic
polypropylene corresponds to a viscosity average molecular weight
greater than about 300,000 (n = 2.0). Alternatively, high molecular
weight is any crystalline polyolefin having an intrinsic viscosity
(n) greater than about 2.0 dl/g. However, for uses other than
papermaking and even for some papermaking applications, the
viscosity average molecular weight employed may be as low as 30,000
to 40,000 i.e., the intrinsic viscosity (n) may be as low as about
1.0 dl/g.
The viscosity average molecular weights referred to herein are
determined by first measuring the specific viscosity of the polymer
in decalin at 135.degree.C., using Ubbelohde No. 50 or 75
viscometers. The viscosity average molecular weight is then
determined by the relationship
(n) = K M.sub.v.sup.a
where
(n) = intrinsic viscosity, and is determined from specific
viscosity by the Schulz and the Blaschke equation.
K = constant, from literature (2.74 .times. K .sup.4 for
polyethylene and 5.43 .times. 10.sup.-.sup.4 for
polypropylene.)
a = constant, from literature (0.81 for polyethylene and 0.65 for
polypropylene.)
The 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 polymer
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, any substituted or unsubstituted aliphatic, aromatic or
cyclic hydrocarbon which is a solvent for the polymer employed at
elevated temperatures and pressures, which is relatively inert
under the conditions of operation and which preferably has a
boiling point at the pressure conditions existing after the
precipitation zone (preferably atmospheric pressure) less than the
softening point of the polyolefin. The solvent may be liquid or
gaseous at room temperature and atmospheric pressure although it is
preferred that it be liquid at such conditions as otherwise the
system after the precipitation zone will have to be pressurized.
Among the solvents which may be utilized are aromatic hydrocarbons,
e.g., benzene, toluene; aliphatic hydrocarbons, e.g., butane,
pentane, hexane, heptane, octane and their isomers and homologues;
alicyclic hydrocarbons, e.g., cyclohexane, chlorinated
hydrocarbons, e.g., methylene chloride, carbon tetrachloride,
chloroform, ethyl chloride, methyl chloride; alcohols; esters;
ethers; ketones; nitriles; amides; fluorinated compounds, e.g.,
fluorohydrocarbons; sulphur dioxide; nitromethane; and mixtures of
the above solvents.
As mentioned previously, the temperature of the solution which is
flashed to evaporate a portion only of the solvent is maintained
above the melt dissolution temperature of the polymer. The melt
dissolution temperature of any particular polymer in a solvent is
easily determined. Low concentrations of the polymer (e.g., 0.1 and
1.0 percent by weight) are placed into the solvent in a vial, which
is sealed and placed in an oil bath. The temperature of the oil
bath is raised slowly (10.degree.C/hr) until the last trace of
polymer disappears. This temperature is the melt dissolution
temperature. For ultra-high molecular weight (about 10 million)
polyethylene at low concentration (0.1 percent by weight) in
cyclohexane, the melt dissolution temperature is 118.5 +
1.9.degree.C. For a dilute solution of high molecular weight
polypropylene in cyclohexane, the melt dissolution temperature is
130.degree.C. At higher concentrations, the melt dissolution
temperature approaches the melting point of the polyolefin.
Lowering of molecular weight lowers the melt dissolution
temperature at a given concentration.
It is preferred to operate between the melt dissolution temperature
and that temperature at which, for the solvent employed, does not
cause vaporization of more than 60-70 percent of the solvent when
the solution is adiabatically fed through a precipitation zone into
a region of reduced pressure. Such maximum temperature for partial
vaporization may be determined for any particular solvent by use of
enthalpy charts. It is preferred to operate at a temperature
sufficiently above the melt dissolution temperature to cause at
least about 20 percent of the solvent to vaporize upon adiabatic
precipitation. For n-hexane, the maximum desirable temperature for
dissolving polyethylene is about 160.degree.C., and the minimum
about 120.degree.C.
Since it is very desirable to have a polymer concentration less
than about 7 percent by weight and preferably less than about 5
percent by weight in the fibrous gel as it enters the mechanical
refining step, it is preferable to operate at a solution
temperature which, for the solvent type and polymer concentration
employed in the solution, does not cause such excessive
vaporization that the polymer concentration in the gel is
substantially greater than about 7.0 percent by weight and
preferably less than about 5 percent by weight. some solvent may be
added to the gel prior to introduction into the refiner if the
consistency is greater than 5 percent by weight to obtain a polymer
slurry having a consistency less than 5 percent, particularly where
use of lower molecular weight polymers permits solutions containing
more than 5 percent polymer concentrations to be employed. However
since it is desirable for the fibers to be in an uncollapsed state
and separated from each other by solvent during refining of the gel
and since added solvent may not function as well in this regard as
that solvent already present in the gel, it is preferable to have
the polymer concentration in the gel less than about 7 percent by
weight so that little additional solvent need be added and, as
stated previously, it is much preferred to operate so that the gel
as precipitated contains less than about 5 percent by weight
polymer. It is most preferred in practice to employ a polymer
consistency of less than about 2.0 percent during refining of the
gel.
In summary, then, the process of the present invention for making a
synthetic pulp for papermaking by discharge of a hot solution of
the polymer from a zone of higher pressure into a zone of lower
pressure, whereby flash evaporation of solvent is effected and
polymer is precipitated, is characterized in that the discharge at
constant rate is effected under parameters of solution
concentration, solution temperature, and pressure of the lower
pressure zone such that only part of the solvent is evaporated and
so much solvent remains in the liquid phase that there is formed a
gel of precipitated polymer in solvent, and further characterized
by mechanical refining of the gel.
The concentration of the hot solution should be within the range
0.5 to 5 percent polymer by weight. The flow rate of the polymer
solution into the reduced pressure zone is 60-120 m/sec. The
proportion of solvent evaporated from the total solvent is
desirably from 20 to about 70 percent; otherwise expressed, the
proportion is desirably such that the ratio of evaporated solvent
to residual liquid solvent is in the range 0.3:1 by weight to 1.5:1
by weight (strictly, evaporation of 23 percent to 66 percent).
The conditions of evaporation are such as to form a gel (suspension
of fibres in solvent) which is capable of being refined to provide
a pulp of the invention as defined above. Thus a further
characteristic of the process of the invention is that the gel
formed by partial evaporation of the solvent contains at most about
7 percent by weight polymer and desirably contains only up to 5
percent by weight polymer and preferably less than 2 percent by
weight. Such a gel is then, according to the invention, refined by
attritional action between proximate surfaces which are in motion
relative to each other.
Before giving specific examples of the pulp and process of this
invention, we describe next a preferred general procedure, together
with some optional process steps which may be adopted with
advantage.
FIG. 1 is a diagrammatic view of an apparatus that may be suitably
employed in the process of the present invention.
FIG. 2 is a cross-sectional view of precipitation zone 22
illustrated diagrammatically in FIG. 1.
FIG. 3 is the enthalpy chart for hexane.
FIGS. 4 to 7 are microphotographs of the fibers produced by the
process of the present invention.
In the pressure-vessel 10 shown in FIG. 1, a solution of the
polymer is heated to desired temperature; if a suspension of
polymer chip, or a slurry of polymer crumb produced by a
low-temperature polymerization process, is used, this suspension or
slurry can be dissolved in vesel 10. Vessel 10 is equipped with a
stirrer 11 and is jacketed whereby heating fluid may be introduced
via conduit 12 and exited via conduit 13. Solvent may be introduced
into the vessel via conduit 14 and a high molecular weight
polyolefin introduced via conduit 15. An inert gas may be
introduced via conduit 16 to maintain the desired pressure in the
vessel. Alternatively, the vessel 10 may be a polymerization
reactor vessel in which an olefin or mixture of olefin, which will
form a crystalline polyolefin, may be polymerized. As a further
alternative, the polymerization may be carried out in another
vessel and the polyolefin solution or slurry fed into vessel 10.
While a solution process would be the preferred method of carrying
out such a polymerization in view of the fact that the polymer
already would be in solution, slurry polymerization procedure could
be employed and the resulting polyolefin suspension or slurry
heated above the melt dissolution temperature of the polyolefin in
vessel 10 to form the solution. The actual polymerization procedure
employed forms no part of the present invention since any such
polymerization procedure conventional in the art can be employed;
it should be noted however that the procedure preferred is a
procedure capable of forming a relatively high molecular weight
polyolefin, as was discussed above.
Once the polyolefin solution is formed in vessel 10, it is fed
through shutoff valve 17 into transfer conduit 18. Transfer conduit
18 is surrounded by jacket 19 into which heating fluid such as
steam is introduced via conduit 20 and exited via conduit 21. The
heating fluid ensures that the polyolefin solution is maintained at
a temperature above the melt dissolution temperature.
The polyolefin solution is then passed through nozzle 22 into
precipitation zone (low pressure zone) 23. During passage of the
polyolefin solution through nozzle 22 the pressure and temperature
of the solution is adiabatically reduced and a portion of the
solvent is vaporized therefrom. The loss of heat effected by this
vaporization cools the residual solution so that the polyolefin
precipitates as a highly swollen fibrous mass or fibrous gel. By
fibrous gel is meant a fibrillar structure of discrete crystalline
polyolefin fibres containing interconnecting capillary spaces
filled with the solvent. The polyolefin content in such gel should
not exceed about 7 percent by weight of the gel; otherwise one is
compelled to dilute the gel with solvent before refining the
gel.
The fibrous gel and the free solvent vapor is then passed through
tubular shear conduit 24. It is believed that some molecular
orientation is imparted during traverse of the gel through the
precipitation zone and conduit 24.
From the tubular shear conduit 24 the fibrous gel passes via
post-precipitation transfer conduit 25 into separation vessel 26
which is maintained at preferably atmospheric or subatmospheric
pressure. Free solvent vapor vaporized during passage of the
polyolefin solution through precipitation zone 33 is separated from
the fibrous gel via conduit 27. The solvent vapor thus removed may
then be condensed and recycled back to vessel 10.
The fibrous polyolefin gel which is in the form of relatively short
"noodles" (preferably less than about 10 cm) caused by solvent
vapor pockets formed during precipitation and which still contains
a substantial amount of solvent drops to the bottom of vapor
separation vessel 26 and from there into disc refiner 28 via
conduit 27. While the process is illustrated as preferably
employing a disc refiner at this stage, alternative apparatus for
imparting attritional forces to the fibrous gel could be employed,
such as are known in the paper-making industry and discussed
above.
The polymer gel is fed into disc refiner 28, and discrete polymer
fibers separated or liberated therefrom during passage
therethrough. The fibres and the small amount of separated solvent
drop from the bottom of disc refiner 26 into a receiving vessel
(not shown) via conduit 28. Any separated solvent and some further
non-separated solvent may be filtered, decanted or centrifuged from
the fibers and the solvent remaining on or within the fibers, which
is still a substantial amount, may be removed therefrom by
conventional steam stripping or solvent extraction techniques.
Transfer conduit 18 is not essential to the practice of the present
process; it is merely employed to convey the polyolefin solution
from solution vessel 10 to precipitation zone 22. It could be
removed completely and precipitation zone 22 located on vessel 10.
Transfer conduit 18 is heated in order to maintain the polyolefin
in solution. The dimensions of the transfer conduit 18 are not
critical; however, it is very desirable to employ a diameter such
that there is little or no pressure drop along the tube.
It has been found to be useful to effect some solvent vaporization
before the polymer solution passes through precipitation nozzle 22,
to cause the vapor cutting mentioned above. Such vaporization aids
in the development of the proper length of the fibrous gel noodles
entering vaporization vessel 24. The greater the vaporization, the
shorter the noodle. Such partial vaporization may be effected by
slight heating of transfer conduit 18; the temperature of the
solution is not raised by such heating due to maintenance of
constant pressure conditions. Alternatively, a valve (not
illustrated) may be inserted in transfer conduit 18 somewhere prior
to nozzle 22. However, such partial vaporization should not be
sufficient to effect precipitation of the polymer.
The size of precipitation nozzle 22 should be such as to create
sufficient pressure-drop to cause rapid precipitation of the
polymer and partial vaporization of the solvent. The pressure drop
should be such as to cause violent vaporization of that portion of
the solvent which does vaporize. Such violent vaporization imparts
turbulence and causes the precipitated fibrous gel to break up into
relatively short noodles which is a highly desirable form for
subsequent operations. Such a turbulent flow condition is important
in developing fiber properties. The amount of turbulence necessary
to develop good fiber properties depends at least partially upon
the molecular weight of the polyolefin employed. The lower the
molecular weight, the greater the turbulence must be in order to
subsequently produce fibers of good quality. If low turbulence is
employed with low molecular weight polyolefin (e.g. polyethylene
with M.sub.V = 40,000) the polymer will be precipitated as a powder
rather than as a fiber. It is difficult to quantitize the minimum
degree of turbulence required to produce fibers since it depends on
several variables; in practice the minimum or optimum turbulence is
imparted to the precipitating polymer by adjusting the size of
nozzle 22 which is, in a preferred embodiment, an adjustable
throttling ball valve, to increase the degree of turbulence by
restricting the nozzle to a more narrow opening. This adjustment
can be continued until the gel product becomes fibrous in nature,
and can be optimized to produce fibers having the best
characteristics for the particular end use desired.
A portion of the pressure drop, and thus of the precipitation and
vaporization, occurs in the precipitation conduit 23 located
immediately after precipitation nozzle. While not essential to the
process, precipitation conduit 23 has been found to be desirable to
continue to impart shear stress to the precipitating polymer and to
aid in preventing the formation of continuous strands which are
difficult to process. The length of precipitation conduit 23 is
adjusted to form noodles having a length between about 5 and 15 cm,
preferably less than about 10 cm. If the precipitation conduit is
too long, undesirably long noodles may be obtained. If the noodle
is continuous, there is a tendency for it to become entrained in
the exhaust line of vapor separation vessel 24, and for twisting or
roping to occur in the disc refiner 28. The diameter of
precipitation conduit 23 is preferably not substantially larger
than the full open size of nozzle 22.
After precipitation conduit 23, the fibrous gel is transferred into
vapor separation vessel 24 via post-precipitation transfer conduit
23. The size of the conduit 23 is not critical except its diameter
should be sufficiently large that little pressure drop occurs
during traverse of fibrous gel therethrough. Therefore, very little
additional solvent is vaporized, and the solvent that is removed in
vapor separation vessel 24 is that solvent which was vaporized in
the precipitation zone 23.
From vapor separation vessel 24 the fibrous gel drops into disc
refiner 28 via conduit 27. In order to be able to feed the fibrous
gel through disc refiner 28, the concentration of polymer
(consistency) should be less than about 7 percent by weight,
desirably less than 5 percent and preferably is less than about 2.0
percent by weight. While it is preferred to operate the
precipitation zone under conditions that provide a fibrous gel
having a proper consistency, if the consistency is too high due to
excessive vaporization, additional solvent may be introduced to the
fibrous gel prior to passage through the disc refiner to lower the
consistency to an appropriate level.
Disc refiner 26 may be any conventional disc refiner employed in
the paper industry. However, it has been found desirable to employ
coarse-patterned plates in the refiner to prevent plugging which
seems to occur more frequently with fine-patterned plates. The gap
between the discs should be low, preferably of the order of about
100 to 125 microns. However, this may be adjusted to develop
various fibre properties.
The fibers obtained after refining still contain a substantial
amount of solvent typically 80-98 percent by weight, which may be
removed by conventional techniques such as centrifuging followed by
solvent exchange to water or steam stripping if the fibers are to
be used for making paper by the water laying technique. Steam
stripping may lead to some loss of the very fine structure of the
pulp described above, but not sufficiently to significantly impair
its properties for papermaking. During solvent removal, care should
be taken not to press the fibers together too tightly as solvent
bonding may take place between fibers which is very
undesirable.
If a nonwoven web, such as paper, is to be made by solvent-laying
techniques, then the residual solvent need not necessarily be
removed. Also, it is very desirable that any additional (secondary)
refining of the fibers to further develop their strength properties
to be carried out while the fibers are still present in solvent
rather than in water.
After steam stripping or solvent exchanging the fibers into an
aqueous slurry, the fibers may be processed for papermaking in the
normal manner. The fibers may be screened and/or centricleaned to
remove undesirable polymer chunks. If the fibers are not made into
paper immediately, the aqueous slurry can be thickened to a
consistency of 50-60 percent and stored in wet cake form. If the
fibers are to be shipped, the wet cake can be compacted and
baled.
The fibers are treated with a water dispersing agent, preferably
prior to or during steam stripping to prevent fiber agglomeration
and preferably with polyvinyl alcohol since this material is not
subsequently washed off the fibers to any great extent. The
polyvinyl alcohols employed have a degree of hydrolysis greater
than 77 percent and preferably 88 to 100 percent hydrolysis. The
molecular weight of the polyvinyl alcohol is not critical although
lower molecular weights, i.e., weight average molecular weights of
10,000 to 20,000 are generally preferred. Generally, the polyvinyl
alcohol is employed in amounts of up to about 2 percent by weight
of the fibers.
EXAMPLE 1
Twenty kilograms of high density polyethylene having a viscosity
average molecular weight of 200,000 was dissolved in 2000 liters of
n-hexane at a temperature of 138.degree.C. in a 7000 liter glass
lined vessel to form a solution wherein the polyethylene
concentration was 10.0 grams/liter. The solution was agitated at
about 100 rpm. The pressure in the solution vessel was maintained
at 5.0 kg/cm.sup.2. The polyethylene solution was fed through a
transfer conduit which was slightly heated to maintain the
temperature at 138.degree.C. and the pressure at 5.0 kg/cm.sup.2.
The transfer conduit was 30 meters in length and had an outside
diameter of 25 cm. The solution was then adiabatically passed at a
rate of 800 liters per hour through a 1/2 inch nozzle throttling
ball valve (which was maintained 60-80 percent open throughout the
run) to atmospheric pressure. The material then passed through a
precipitation conduit having a diameter of 0.5 inch and a length of
about 270 mm. From the precipitation conduit the fibrous gel,
having a temperature of about 70.degree.C. and at atmospheric
pressure passed into a post-precipitation transfer conduit which
was 2 inches in diameter. The fibrous gel then passed into a vapor
separation vessel (cyclone) which removed vaporized hexane from the
top thereof. About 50 percent by weight of the hexane was
vaporized. The fibrous gel noodles (which were less than about 10
cm. in length) containing about 3 percent by weight polyethylene
were collected in the bottom, from which they were passed along
with enough added hexane to give a consistency of about 1 percent
by weight polyethylene through a single disc refiner having 12 inch
discs with medium coarse plates. The refiner was operated at 2000
rpm. The refined fibrous slurry was then collected in a glass lined
vessel and recirculated through the refiner for a total of four
passes. The fiber slurry at 1.0 percent consistency was then pumped
through a filter and the resulting wet cake having a consistency of
13 percent was fed into a 2000 liter glass lined steam stripping
vessel along with 1500 liters of water and 150 grams of polyvinyl
alcohol having a molecular weight of 10,000 and 94 percent
hydrolyzed (to aid dispersion) and the remaining hexane steam
stripped from the fibers at a temperature of 60.degree.C. The
resulting aqueous slurry of polyethylene fibers at a consistency of
1 percent was then centrifuged to remove water and provide a wet
fiber cake at about 50 percent oven dry consistency.
The fibers thus produced had a gas adsorption surface area of 4.8
m.sup.2 /g.
The fibers were fractionated on Tyler standard screens in
accordance with TAPPI Test T 233 SU 64 and the following fiber
fractions obtained:
TABLE 1A ______________________________________ Mesh Weight %
Length (mm) Coarseness (decigrex)
______________________________________ On +20 mesh 6.9 1.88 31.3 On
+35 32.7 1.54 15.9 On +65 25.2 1.18 13.1 On +150 18.1 On +270 7.3
Thru 270 9.8 ______________________________________
Two sets of standard handsheets were prepared, one set from 100
percent of the fibers and one set from a 50 percent by weight blend
of the fibers and 400 Canadian Standard freeness bleached alder
kraft cellulose fibers. The handsheets, having a basis weight of
about 37 pounds/3,000 sq. ft. were formed on a British sheet
machine using the 150-mesh stainless steel screen in accordance
with TAPPI Test T205 M-58. The sheets were couched from the screen
or wire in the standard manner and subjected to a 15-second cold
(70.degree.F.) press at 100 psi against a polished caul. The sheets
were given a second identical press after turning them over on the
caul so that both sides of the handsheet were given a smooth
finish. The final drying was done on a rotary dryer at
220.degree.F. The sheets were then tested for strength and optical
properties in accordance with standard TAPPI testing methods:
TABLE 1B ______________________________________ Property 100% PE
Fiber 50% Blend* ______________________________________ Basis
weight (lbs./3000 ft..sup.2) 39.79 38.3 Caliper (mils) 10.3 7.0
Density (g/cc) 0.248 0.350 Tear (g/sheet) 4.8 27.0 Breaking Length
(meters) 13.6 2856 Tensile (lbs./inch) 0.29 5.9 Stretch (%) 1.5 2.5
TEA (ft.-lb./ft..sup.2) 0.027 1.2 Scott Internal Bond 11.0 42.0
TAPPI opacity (%) 93.6 87.2 Brightness (Elrepho 8) 84.8 87.9
______________________________________ *Wet pressed at 60 psi.?
The fibers were further blended with 400 Canadian Standard freeness
bleached alder kraft as 40 percent and 80 percent by weight blends
and the blends formed into paper on a small papermachine, and the
resulting paper webs tested for strength and optical properties as
above. These tests, which more nearly correspond to actual
commercial papermaking indicate that strength properties are higher
than for handsheets:
TABLE 1C ______________________________________ Property 40% Blend
80% Blend ______________________________________ Basis weight
(lbs./3000 ft..sup.2) 33.8 33.6 Caliper (mils.) 3.4 5.3 Density
(g/cc) 0.636 0.405 Tear (g/sheet) WMD 32 26 CMD 34 28 Tensile
(lbs./inch) WMD 16.0 5.6 CMD 8.5 4.0 Stretch (%) WMD 1.5 2.9 CMD
3.2 0.6 TEA (ft.-lb./ft..sup.2) WMD 1.8 1.3 CMD 2.5 2.5 Scott
Internal Bond 121 187 TAPPI opacity (%) 75 68 Brightness (Elrepho
8) 80 85 ______________________________________ NOTE: WMD is with
machine direction; CMD is cross machine direction.
EXAMPLE 2
This example illustrates the preparation of fibers in accordance
with the present invention from high density polyethylenes of
various viscosity average molecular weights. The procedure of
Example 1 was substantially repeated for the various polyethylenes.
Process details are set forth in Table 2A below, the fiber
fractionation results are set forth in Table 2B below and handsheet
properties are set forth in Table 2C below. In all cases, hexane
was added to the gel prior to refining to lower the consistency to
about 1 percent by weight polyethylene.
TABLE 2A
__________________________________________________________________________
Process RUN NUMBER Conditions 1 2 3 4 5 6 7
__________________________________________________________________________
Mv (X 10.sup..sup.-3) 40 65 100 200 300 400 600 PE, kg 120 22.5 20
20 15 15 20 Hexane, 1 2000 1500 2000 2000 2000 2000 2000 PE g/1 60
15 10 10 7.5 7.5 10.0 Temp. (.degree.C) 140 141 140 141 140 138 139
Press (kg/cm.sup.2) 5.0 5.5 5.0 5.1 5.1 5.3 5.8 Refining (passes or
hours recycle) -- 2 hrs. 2 hrs. 4 passes 1.75 hrs. 2 passes 3
passes % PVA 2.0 1.0 1.0 -- 1.0 2.0 2.0 Steam strip Temp.
(.degree.C) -- 63 63 63 63 80 80 Gel consistency (wt %) 15.4 4.4
3.0 3.0 2.2 2.2 3.0
__________________________________________________________________________
TABLE 2B
__________________________________________________________________________
RUN NUMBER Screen Mesh 1 2 3 4 5 6 7
__________________________________________________________________________
On 20 0.6 0.1 0.9 1.6 0.1 8.3 7.9 On 35 0.1 3.4 5.4 13.0 5.7 21.6
24.9 On 65 14.0 14.5 22.0 25.5 28.0 27.9 28.0 On 150 35.3 36.2 37.3
32.9 36.1 21.8 18.1 On 270 24.4 21.2 15.8 15.8 10.4 8.1 2.7 Thru
270 25.6 24.6 18.6 11.2 19.7 12.3 18.4
__________________________________________________________________________
TABLE 2C
__________________________________________________________________________
RUN NUMBER Property 1* 2 3 4 5 6 7
__________________________________________________________________________
Basis Weight 35.7 37.6 38.6 39.6 37.6 38.7 41.6 Caliper 4.4 6.9 7.2
10.4 6.7 11.5 12.3 Density 0.52 0.35 0.34 0.245 0.36 0.216 0.216
Tear 20 3.0 3.0 3.2 5.0 3.0 3.2 Breaking Length 2249 86 111 155 223
-- -- Tensile 7.3 0.29 0.39 0.33 0.77 0.249 -- Stretch 2.4 0.82 1.5
2.0 1.8 2.8 2.6 TEA 1.2 0.02 0.04 0.049 0.11 0.055 0.065 Scott
Internal Bond 70.0 11.0 15.0 12.0 16.0 15.0 6.0 Opacity 85.4 90.0
91.3 93.6 94.9 91.7 93.0 Brightness (Elrepho 8) 82.3 90.3 88.7 87.6
86.9 89.1 90.4
__________________________________________________________________________
*50/50 Blend - 100% sheets stuck to wire.
It is seen from the foregoing example 2 that an increase in
molecular weight generally provides improved handsheet
properties.
EXAMPLE 3
This example illustrates operation of the present pregress under
different temperature conditions. The solvent employed was
n-hexane. The procedure of example 1 was generally followed. Table
3A sets forth specific process conditions, Table 3B sets forth
fiber fractionation results and Table 3C provides handsheet
properties.
TABLE 3A ______________________________________ RUN NUMBER Process
Conditions 1 2 3 4 5 ______________________________________ Temp.
(.degree.C) 132 136 138 140 142 Press (kg/cm.sup.2) 4.8 5.4 5.7 5.7
5.1 M.sub.v (X 10.sup..sup.-3) 600 600 600 600 200 PE, kg 22.5 22.5
22.5 30.0 20.0 Hexane, 1 3000 3000 3000 3000 2000 PE g/l 7.5 7.5
7.5 10.0 10.0 Refining, passes 3 3 3 4 4 % PVA 2.0 2.0 1.0 2.0 1.0
Steam strip Temp. (.degree.C) -- 80 80 80 63 Gel consistency, 2.2
2.2 2.2 3.0 3.0 wt. % ______________________________________
TABLE 3B ______________________________________ RUN NUMBER Mesh 1 2
3 4 5 ______________________________________ On 20 3.9 1.1 4.4 2.2
2.2 On 35 16.9 7.3 14.1 3.8 8.7 On 65 27.4 24.9 28.9 30.9 24.9 On
150 22.1 34.5 27.7 29.2 38.6 On 270 9.7 18.1 7.8 13.0 16.1 Thru 270
20.0 14.1 17.1 20.9 9.5 ______________________________________
TABLE 3C ______________________________________ RUN NUMBER
Handsheet Property 1 2 3 4 5 ______________________________________
Basis Weight 38.0 38.1 37.1 36.0 35.0 Caliper 10.29 10.33 10.0 9.91
6.0 Density 0.236 0.236 0.237 0.232 0.376 Tear 5.0 3.0 3.0 3.0 3.8
Breaking Length -- -- -- -- 233 Tensile 0.380 0.424 0.271 0.406
0.74 Stretch 2.4 2.3 2.5 3.1 1.1 TEA 0.067 0.098 0.050 0.099 0.056
Scott Internal 15.0 13.0 12.0 13.0 24.0 Bond Tappi Opacity 94.1
95.1 94.2 93.3 93.6 Brightness (Elrepho 8) 87.8 88.4 92.7 92.6 89.1
______________________________________
The importance of the maximum temperature limitation previously
discussed can perhaps be best illustrated by reference to FIG. 3
which is a graph of the enthalpy of hexane, the solvent employed in
foregoing example 3. As can be seen by reference to this graph, if
the solution temperature exceeds about 188.degree.C. (point A on
the saturated liquid curve), upon precipitation of the polymer all
of the solvent is in the vapor phase and none in the liquid phase
since the temperature of the precipitated polymer would be
substantially the boiling temperature of hexane (68. 3.degree.C) at
atmospheric pressure, corresponding to point B on the saturated
vapor curve of the graph. Therefore, the solution temperature
employed should be less than the temperature on the saturated
liquid curve (point A) corresponding (at constant enthalpy) to the
point on the saturated vapor curve (point B) representing the
boiling point of the solvent. The temperature chosen therefore
should be less than that of Point A so a portion of the solvent
will be in the liquid phase, and depends upon the polymer
concentration in the starting solution, keeping in mind that the
polymer concentration in the fibrous gel should not exceed about 5
percent by weight.
For example, since it is desirable that the polymer concentration
in the gel not exceed about 5 percent by weight, and since the
maximum concentration of polymer in the solution employable with
the high molecular weight polymers described herein is about 2
percent, the solvent should not vaporize in excess of about 60-70
percent at that concentration level. By reference to FIG. 3, and
for hexane as the solvent, it is seen that this maximum
vaporization corresponds to a temperature of about 160.degree.C.
(see line C-D), since the portion of line C-D to the left of the
boiling point of hexane ordinate represents to the liquid phase
portion (about one-third of line C-D) and the portion of line C-D
to the right of the boiling point ordinate represents the vapor
phase (about two-thirds of line C-D).
A similar analysis will provide maximum solution temperatures
usable in the present process for other solvent and/or other
pressure conditions.
EXAMPLE 4
This example sets forth typical valves of hydrodynamic surface
area, compressibility constant and drainage time of the fibers of
the present invention. Some of the fibers are those produced by
earlier examples. All fibers were treated with 2 percent PVA added
during steam stripping as in Example 1.
TABLE 4A ______________________________________ Drainage Resistance
Characteristics Example Run No. No. S V M N DT DF
______________________________________ 1 -- 0.65 2.21 0.0045 0.291
-- 0.22 2 1 0.81 2.24 0.0124 0.218 5.3 0.65 2 2 0.70 1.83 0.0101
0.245 5.1 -- 2 3 0.79 1.88 0.00595 0.283 -- 0.41 2 5 -- -- -- -- --
0.69 2 7 0.72 2.66 0.0045 0.291 -- 0.31 4 1 0.88 1.95 0.0072 0.266
5.5 -- 4 2 0.83 1.88 0.00695 0.270 -- -- 4 3 0.93 2.03 0.00635
0.274 5.7 -- 4 4 0.98 2.24 0.00521 0.287 -- --- Note: S =
hydrodynamic surface area, m.sup.2 /g. V = hydrodynamic volume,
cc/g. M & N = compressibility constants DT = drainage time,
seconds DF = drainage factor, seconds/gram
______________________________________
The polyethylene fibers designated Example 4, runs 1-4 in Table 4
above were made by the procedure set forth in Example 1, with the
following specific condition differences:
TABLE 4B ______________________________________ Polyethylene Run
No. Mv n Solution Concentration Temperature in Solution
______________________________________ 1 220,000 2.6 140.degree.C
10 kg/m.sup.3 2 220,000 2.6 140.degree.C 10 kg/m.sup.3 3 820,000
6.2 137.degree.C 7.5 g/l 4 65,000 2.2 141.degree.C 15 g/l
______________________________________ Note: Runs 1, 2 and 4 were
refined for 2 hours, recycling. Run 3 was refined by 4 passes
through the refiner.
EXAMPLE 5
This example illustrates the preparation of a fibrous gel suitable
for subsequent refining into discrete fibers. A 3 percent by weight
polymer solution was prepared by dissolving polyethylene having a
viscosity average molecular weight of 400,000 (n = 9.4) produced by
Ziegler method into hexane at 135.degree.C. The dissolution vessel
containing this polymer solution was connected with a reduced
pressure vessel (receiving vessel) which was at atmospheric
pressure, through a pipe of 5 cm. diameter. A valve was attached to
this pipe a short distance from the dissolution vessel.
The polymer solution was then transferred to the reduced pressure
vessel by opening the valve. The flow rate of the solution between
the valve and the reduced pressure vessel was 80 m./sec. at steady
state and the vapor-liquid ratio of hexane was 1/1.
The fibrous gel material produced had a noodle length of 5 cm., a
diameter or thickness of 50 .mu., and the fibers therefrom had a
gas adsorption surface area of 80 m.sup.2 /g and a strength of 2
g./d.
EXAMPLE 6
This example illustrates the preparation of a polypropylene gel
suitable for subsequent refining into discrete fibers. A 3 percent
by weight solution was prepared by dissolving polypropylene having
an intrinsic viscosity of 5.2 into benzene at 135.degree.C. The
resulting polymer solution was discharged into an atmospheric
pressure according to the same method as in Example 5. The flow
rate of the mixture was 85 m./sec. and the vapor-liquid ratio of
benzene was 1.5/l.
The fibrous gel noodle material obtained had an average shape
measuring 7 cm. in length, 35 .mu. in diameter or thickness, and
the fibers therefrom had a gas adsorption surface area of 30
m.sup.2 /g and a strength of 1.5 g./d.
EXAMPLE 7
A fibrous polypropylene gel as prepared in Example 6 diluted to a
consistency of 2 percent by weight was refined by passing it once
through a disc refiner with the plates 0.003 inch apart. The
refined fibers were then placed into a waring blender and exchanged
to water through isopropanol, accomplished by first adding 100
percent isopropanol, filtering, adding 50/50 isopropanol/water,
filtering and finally dispersing in 100 percent water. Potato
starch (5 percent by weight of the fibers) was added to the water
to render the fibers water dispersible. The fibers thus produced
had a gas adsorption surface area of 1.5 m.sup.2 /gram.
Standard handsheets were prepared from 100 percent of the
polypropylene fibers thus prepared in accordance with TAPPI Test T
205 m-58 and as disclosed in Example 1. The sheets were then tested
in accordance with standard TAPPI testing methods and the following
properties noted:
TABLE 5 ______________________________________ Basis weight
(lbs/3000 ft.sup.2) 35 Tensile (lbs/inch) 1.4 Tear (grams/sheet)
16.4 Breaking length (meters) 440 Stretch (%) 3.0 TEA
(ft-lbs/ft.sup.2) 37.0 Scott Internal Bond 286 Brightness (%) 84.5
TAPPI opacity (%) 92.9 Scattering coefficient 76.4
______________________________________
* * * * *