U.S. patent number 3,920,507 [Application Number 05/353,859] was granted by the patent office on 1975-11-18 for process of making polyolefin fibers.
This patent grant is currently assigned to Crown Zellerbach Corporation. Invention is credited to Hayato Yonemori.
United States Patent |
3,920,507 |
Yonemori |
November 18, 1975 |
Process of making polyolefin fibers
Abstract
An improved process of manufacturing fibers by the technique of
forming a mixture of polymer, solvent for such polymer and,
optionally, water or other flashing aids, at a temperature (flash
temperature) which is high enough to bring the polymer to a plastic
state and which will permit substantially complete vaporization of
the solvent when the mixture is flashed, flashing the mixture into
a flash zone to produce a fibrous product and subsequently refining
the fibrous product characterized in that the fibrous product is
first cooled prior to passing it through a primary refining zone.
The primary refining is effected under conditions that impart a
vigorous fibrillating action to the fibrous product and provides a
pulp having a drainage factor in excess of 1.0 seconds/gram.
Inventors: |
Yonemori; Hayato (Iwakuni,
JA) |
Assignee: |
Crown Zellerbach Corporation
(San Francisco, CA)
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Family
ID: |
26969064 |
Appl.
No.: |
05/353,859 |
Filed: |
April 23, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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295339 |
Oct 5, 1972 |
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Current U.S.
Class: |
162/157.5;
162/164.1 |
Current CPC
Class: |
D01D
5/11 (20130101); D21H 13/14 (20130101); D21H
5/202 (20130101) |
Current International
Class: |
D01D
5/00 (20060101); D01D 5/11 (20060101); D21F
011/00 () |
Field of
Search: |
;162/157R,157C,164,168,146 ;264/5,13,14,121,205,209 ;260/94.9F |
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.
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATION
This is a continuation-in-part of application Serial No. 295,339
filed October 5, 1972.
Claims
I claim:
1. In a method of producing a pulp of polyolefin fibers wherein an
aqueous dispersion of a polyolefin in a solvent at an elevated
temperature and pressure is flashed through a nozzle into a zone of
reduced pressure to form a fibrous product, the improvement
comprising dissolving in the aqueous phase of the dispersion from
0.75 to 10% by weight polyvinyl alcohol based on the weight of the
polyolefin flashing said dispersion to form the fibrous product and
passing the fibrous product at a temperature between about
10.degree.C and 60.degree.C through a primary refining zone under
substantially atmospheric pressure in the presence of the polyvinyl
alcohol under conditions such that a vigorous fibrillating action
is imparted to the fibrous product.
2. The process of claim 1 wherein the fibrous product is diluted
with water to a consistency between about 1% and 10% by weight
prior to refining.
3. The process of claim 1 wherein refining is carried out by
passing the fibrous material through a disc refiner with the
spacing between the discs set at between about 0 and 2500
microns.
4. The process of claim 3 wherein the discs are rotated at a
relative velocity between about 4000 and 8000 feet/minute.
5. The process of claim 1 wherein the fibrous product is subjected
to a total power greater than about 0.2 kilowatt-hour/kilogram
during refining.
6. The process of claim 1 wherein the polymer is an at least
partially crystalline polyolefin.
7. The process of claim 1 wherein the polyolefin is
polyethylene.
8. The process of claim 1 wherein the primary refining is carried
out under conditions to impart a vigorous fibrillating action to
the fibrous product effective to produce a pulp having a drainage
factor greater than 1.0 second/gram.
9. The process of claim 1 wherein the primary refining is carried
out under conditions to provide a pulp less than 90% by weight of
which is retained on a 20 plus 35 mesh Tyler screens when passed
therethrough at a consistency of 0.5% by weight.
Description
BACKGROUND OF THE INVENTION
Numerous process have been proposed for preparing synthetic fibrous
materials by flashing polymer solutions or dispersions held at high
temperature and pressure into a zone of reduced pressure. In
various patent literature, such as German Offenlegungsschrift No.
1,958,609 and Japanese patent application No. 71-34921, processes
are proposed in which a polymer is dissolved in a solvent therefor
and heated under at least autogenous pressure and then flashed into
a zone of lower pressure to thereby vaporize the solvent and form
fibrous materials. In the latter mentioned patent, the fibrous
material thus formed is quenched with a water spray at a
temperature between 60.degree.C and 80.degree.C.
Similar processes are presented in U.S. patent application Ser. No.
295,339 filed Oct. 5, 1972, (assigned to the assignee of the
present application) and as well in German OLS No. 2,121,512 and
German OLS No. 2,144,409. In these processes a polymer dissolved in
a solvent is mixed with water or other liquid non-solvents for the
polymer to form an emulsion of the polymer solution in a continuous
water phase and this emulsion is heated and flashed to reduced
pressure zone to produce fibers.
Another approach is described in U.S. patent application Ser. No.
285,386, filed Aug. 30, 1973, and now abandoned (assigned to the
assignee of the present application) wherein a polymer solution in
which water is dispersed as a discontinuous phase is flashed to
form fibers. In this process, the water concentration is held
between 30% and 70% of the entire mixture and in forming the
mixture is preferable to add the water to the preformed polymer
solution to insure that the water forms the discontinuous
phase.
OLS No. 2,117,461 describes a process in which molten polymer is
emulsified with water (optionally, with a minor amount of solvent
in the polymer phase) and then heated and flashed to a reduced
pressure zone to form fibers.
While many variations are evident, it is seen that the common
features of all these fiber-making processes is the flashing into a
zone of reduced pressure of a heated mixture containing a polymer
and a solvent for such polymer. Various conditions of flashing are
suggested in the referenced processes including temperature and
pressure ranges for the mixture to be flashed and various solvents,
flashing aids, etc. Most of the references contemplate flashing
into a zone held at atmospheric pressure. Others suggest the
possibility of flashing into a zone which is above or below
atmospheric pressure, in some case with the application of heat in
such zone. All of the processes may lead to the production of
fibrous material. However, each suffers from the shortcoming that a
specific set of conditions of flashing, particularly with regard to
temperature and pressure, and inter-relationship of such conditions
are not provided which will permit manufacture, in a practical
manner, of fibers having the optimum properties desirable for their
use as a synthetic pulp in the manufacture of paper by conventional
techniques.
Fibrous materials produced under the general process conditions
described in these references tend to be interconnected or bundled
together to an undesirable degree and the paper produced therefrom
is undesirably low in strength (e.g., tensile strength). Such
fibrous material is more difficult to separate, cut or refine in
preparation for papermaking and contains a high content of gels and
chunks of polymer which cause undesirable "fish eyes" or
transparent spots in paper manufactured therefrom.
It has recently been suggested (in a U.S. patent application Ser.
No. 340,140 of H. Yonemori filed by the present assignee on Mar.
12, 1973 and entitled "Process of Making Fibers") to overcome these
problems by providing a specific interrelated set of flashing
conditions to produce a product capable of being readily separated
and refined into an improved pulp for papermaking which has a low
content of gels and chunks and excellent drainage factor
characteristics. Briefly, that process comprises a flashing into a
zone at subatmospheric pressure to provide a fibrous product having
a temperature less than 70.degree.C and subsequently refining the
pulp at this low temperature, preferably while maintaining the pulp
under such subatmospheric conditions in order to prevent
condensation of solvent vapor. While this approach is completely
satisfactory from a technical point of view, it is expensive to
practice commercially because of the vacuum requirements imposed on
the system.
It has been suggested (in a U.S. patent application of J. Kozlowski
recently filed by the present assignee entitled "Process of Making
Fibers") to obtain a fibrous pulp having high drainage
characteriztics by maintaining the flashed product at a temperature
above the boiling point of the solvent (preferably between
70.degree.C and 100.degree.C) subjecting the fibrous produce to a
primary refining that comprises a light defibering or shredding
action, and subjecting the pulp to a vigorous fibrilating action in
a secondary refining zone.
In Netherlands application No. 72/10567 published Feb. 3, 1973 it
is disclosed that a fibrous gel material containing large amounts
of solvent is first subjected to disc refining in the presence of
the solvent to develop the fibers, followed by steam stripping the
solvent from the fibers in an aqueous slurry in the presence of
polyvinyl alcohol.
BRIEF DESCRIPTION OF THE PRESENT INVENTION
The purpose of the present invention is to provide an economical
technique applicable to all of the flashing processes previously
described which will produce a pulp useful for producing synthetic
paper by conventional papermaking techniques which has surprisingly
improved properties and a low content of gels and chunks. The
present process obviates the need for refining under subatmospheric
pressure.
Briefly the present process comprises taking the flashed fibrous
product produced by any of the foregoing processes, forming an
aqueous slurry of the fibrous product at a temperature between
about 10.degree.C and 60.degree.C, and passing the fibrous product
at such a temperature through a primary refining zone operated
under conditions such that the fibrous product is subjected to a
vigorous refining or fibrillating action. The resulting pulp has a
drainage factor in excess of 1.0 second/gram and as high as 200
seconds/gram or higher.
DESCRIPTION OF PREFERRED EMBODIMENTS
In practicing the process of the present invention, any polymer or
copolymer may be employed which is capable of forming fibers by
conventional spinning techniques. It is preferred to employ
crystalline or partially crystalline polyolefins such as low
pressure polyethylene, isotactic or partially isotactic
polypropylene, and ethylene-propylene copolymers. Additionally,
polybutenes and polymethyl pentenes may be employed in the practice
of this invention. Crystalline or partially crystalline polyamides
and polyesters may also be used. Noncrystalline polymers such as
polycarbonates, polysulfones, polyvinyl chloride,
polymethyl-methacrylate, polyacrylonitrile and polystyrene may be
used. Mixtures of the foregoing with each other or other polymers
may also be employed.
The preferred polyolefins employed are those having an intrinsic
viscosity above about 0.7 dl/g., which for high density
polyethylene corresponds to a viscosity average molecular weight of
about 30,000 to 40,000.
The polymers employed in practicing the present process may be in
the form of dried powder or pellets or, prefereably, as a wet cake,
slurry or solution of polyolefin in the reaction solvent as
obtained after polymerization.
Generally, any substituted or unsubstituted aliphatic, aromatic or
cyclic hydrocarbon which is a solvent for the polymer at elevated
temperatures and pressures, which is relatively inert under the
conditions of operation and which has a boiling point at
atmospheric pressure that is between 20.degree.C and 130.degree.C,
preferably between 50.degree.C and 100.degree.C, and at the flash
zone pressure (substantially atmospheric) that is less than the
softening point of the polymer may be employed in practicing the
present process. Illustrative of the solvents which may be utilized
are aromatic hydrocarbons, e.g., benzene; aliphatic hydrocarbons,
e.g., pentane, hexane, heptane and their isomers and homologues;
alicyclic hydrocarbons, e.g. cyclohexame; chlorinated hydrocarbons,
e.g. methylene chloride, carbon tetrachloride and chloroform;
higher alcohols; esters; ethers; kestones; nitriles, amides;
fluorinated compounds, e.g. fluoro-hydrocarbons; nitro-methane; and
mixturee of the above solvents and other solvents having a boiling
point between about 20.degree.C and 100.degree.C at atmospheric
pressure. The preferred solvent is hexane which has a boiling point
of 68.7.degree.C at atmospheric pressure.
The polymer-solvent mixture may be formed by any one of several
methods. One may start with a solution of polymer in solvent as it
comes from a solution polymerization process, either at the same
concentration, diluted or concentrated. Alternatively, one may
start with a slurry of polymer particles in the solvent such as is
produced by a slurry of polymerization procedure and the
appropriate amount of water is added to the slurry of vice versa. A
further alternative would be to start with a dry polymer powder, or
granules, or a wet cake such as might be produced at some stage of
solvent removal in the polymer plant and the appropriate amount of
solvent is admixed therewith.
The polymer concentration relative to the solvent is not critical,
the solvent being present in an amount that is greater than 100% by
weight of the polymer and sufficient to give a viscosity at the
flash temperature employed that can be easily handled. Frequently
this viscosity will be up to 3,500 centipoises. Generally the
polymer concentration will vary from about 2% to about 30% by
weight of the solvent plus polymer, and preferably is in the range
of about 5% to about 15%.
In one preferred embodiment water is employed as a flashing aid. In
this embodiment the water may in a continuous phase or
discontinuous phase, depending upon the amount of water added to
the polymer-solvent mixture and the manner of addition. If the
water is to form the discontinuous phase it should be present in an
amount less than 70%. To form a continuous water phase the water
should be present in an amount greater than 30% by volume of the
mixture and preferably between 50% and 70%. The particular method
of mixing is not critical, but if it is desired to have the water
form a discontinuous phase it has been found to be advantageous to
have the solvent present prior to water addition since the solvent
or polymer solution will form the continuous phase of the mixture
to be formed. This latter approach is particularly desirable when
one employs an amount of water which is neat the borderline of an
inversion occurring, i.e., at the point where the amount of water
is approaching that level where it would form the continuous phase.
Conversely, if the water is added with or before the solvent, it
will tend to form the continuous phase.
A primary function of the water is to provide energy to aid the
vaporization of the solvent during flashing since it is not
desirable to have the temperature so high that there is sufficient
energy imparted to the solvent alone to effect its complete
vaporization. However, the amount of water should not be so great
as to require the expenditure of unnecessary heat values in
attaining the desired flashing temperature, i.e., once that amount
of water required to form an aqueous solution or dispersion of the
agent having a suitable viscosity is determined, additional water
may be employed to a certain extent since it helps to lower the
mixture viscosity and aid solvent vaporization but the additional
amount need not be great.
Another function of the water is to reduce the temperature of the
fibrous mass in the zone immediately following the nozzle (flash
zone). The addition of water increases the total vapor pressure of
the system at the moment of flashing, thus reducing the boiling
point of the flashing mixture. This is independent of the amount of
water employed, and very small quantities may thus be employed for
this purpose. As a practical matter, however, water would be
employed in the amount of at least about 1% by volume of the
solvent-water mixture. Lowering the boiling point of the mixture in
this fashion will assist in establishing proper temperature
conditions in the fibrous mass formed upon the flashing in
accordance with this invention, as discussed in detail at a later
point.
Another function of the water is to act as the carrier for a
hydrophilic water-dispersing agent for the fibers to be formed. It
has been found that it is most advantageous to have the
water-dispersing agent present during flashing and precipitation of
the fibrous polymer. An equivalent amount of the same agent added
at a later stage to the already formed fibers does not give the
same degree of dispersibility and the presence of the agent
enhances the refinability of the fibers. Therefore, ,the water
should be present in an amount sufficient to carry that amount of
the hydrophilic agent employed to impart to the fibrous polymer the
desired level of water dispersibility, preferably as a solution
thereof. Additional water above such minimum amount required to
carry the agent may be employed to impart a suitable viscosity to
the aqueous solution or dispersion agent, i.e., the aqueous
solution of the water-dispersion agent should not be so viscous as
to present problems of handling or incorporation into the polymer
solution as a dispersed phase. Also, the water can aid in reducing
the viscosity of the mixture to a level less than that of the
polymer solution alone, thus permitting higher polymer
concentrations.
The agents which may be added to the mixture to impart water
dispersibility to the fibrous polymer are preferably water-soluble
or partially water-soluble high molecular weight materials.
However, they may also be materials which are soluble or partically
soluble in the solvent so long as they are somewhat hydrophilic and
impart water dispersibility to the fibers. The amount of
water-dispersing agent employed may range from about 0.1% to about
15% by weight of the polymer, preferably from about 0.1% to about
5% by weight. The preferred water-dispersing agent is an at least
partially water-soluble polyvinyl alcohol (PVA) having a degree of
hydolysis greater than about 77% and, preferably, greater than
about 88 mol.% having a viscosity (in a 4% aqueous solution at
20.degree.C) between about 2 and 50 centipoises. Desirably the PVA
has a degree of polymerization in the range of 200 and 4000 and
preferably between 300 and 1500. If desired, the PVA may be
chemically modified to enhance its adhesion to the polymer,
dispersion and other properties. The polyvinyl alcohol is
preferably added with the water at the time the mixture is formed.
Illustrative of other water-dispersing agents that may be employed
are cationic guar, cationic starch, potato starch, methyl cellulose
and Lytron 820 (a styrene-maleic acid copolymer).
The use of polyvinyl alcohol is important in developing the fiber
properties during refining of the flashed product in accordance
with this invention as described at a later point. For this
purpose, the polyvinyl alcohol may be added subsequent to flashing,
such as with the dilution water for refining. It is particularly
advantageous to add at least 0.75% and preferably between 11/2% and
5% by weight of the flashed polymer of polyvinyl alcohol, either
before and/or after flashing (but prior to refining). If polyvinyl
alcohol is not present during refining, the refining can be carried
out only with difficulty, if at all, and the properties of the
resulting pulp and sheets made therefrom are very poor.
The ingredients of the mixtures can be placed in any suitable
vessel which is capable of being heated to an elevated temperature
and pressure. Generally, an autoclave is employed. However, when
water is added as a flashing aid it is important that the vessel
employed be equipped with a mixing or stirring device capable of
keeping the mixture in a constant state of agitation since a stable
emulsion is not formed and upon standing the mixture will quickly
separate into two distinct and separate phases.
The ingredients are then heated to a suitable temperature and
preferably agitated if water is present to form a uniform mixture
wherein water is present as a discontinuous or dispersed phase
within a continuous phase of polymer solution or as a continuous
phase with polymer solution dispersed uniformly therein, depending
upon the water concentration and mode of addition as previously
discussed. The temperature employed is preferably above the melt
dissolution temperature of the polymer in the solvent employed. The
melt dissolution temperature of any particular solvent is
determined by placing low concentrations of the polymer (e.g., 0.1
and 1.0% by weight) into the solvent in a vial which is then sealed
and placed in an oil bath. The temperature of the oil bath is
raised slowly (e.g., 10.degree.C/hour) until the last trace of
polymer disappears This temperature is the melt dissolution
temperature. In some instances, it may be desirable to operate at a
temperature below the melt dissolution temperature. In this case
the temperature sould be high enough under the operating conditions
so that the polymer is dissolved in the solvent or at least is in a
swollen state with sufficient fluidity to be discharged from the
nozzle, i.e. in a plastic state.
Flashing is preferably carried out substantially adiabatically,
utilizing the heat (enthalpy) in the heated mixture to provide the
heat of vaporization for vaporizing substantially all of the
solvent when the mixture is discharged to the flash zone held at a
suitable lower pressure. Accordingly, for adiabatic flashing the
temperature of mixture prior to flashing should be high enough to
provide sufficient heat content or enthalpy for vaporization
adiabatically of substantially all solvent upon flashing to the
flash zone. However, the maximum temperature employed should be
less than the critical temperature of the solvent and/or the
decomposition temperature of the polymer.
It is also possible to carry out the flashing to some extent in a
non-adiabatic fashion, for example, by the addition of heat to the
material as it is flashed from the nozzle. For instance, low
pressure steam (e.g., below 20 psig) or water at about 100.degree.C
may be added to the fibrous noodle in the flashing zone as by
injection thereof in a conduit immediately following the flash
nozzle into which the flashed noodle is also injected. In this
case, the flashing temperature should be chosen so that the heat
content in the mixture to be flashed plus the heat added to the
flashed material is sufficient to vaporize substantially all of the
solvent in the flash zone.
The pressure employed in the vessel containing the heated mixture
is preferably substantially autogenous although pressures higher
than autogenous may be employed. It may be desirable, particularly
in batch operations, to employ an inert gas such as nitrogen during
the flashing operation to maintain substantially autogeneous
pressure in the vessel and thus maintain the velocity of the
mixture through the nozzle at a fairly constant level.
Flashing is preferably effected through a nozzle which has a
substantial longitudinal dimension in order to efficiently impart
shear to the mixture (particularly the polymer component thereof)
immediately prior to flashing. Such shearing action aids fiber
formation and enhances fiber properties for papermaking purposes.
The nozzle may be circular or noncircular in cross-section and may
be an annulus.
The flash zone is maintained at a pressure which, in conjunction
with the other conditions of flashing are selected so that the
temperature of the flashed product is almost immediately lowered in
the flash zone, by evaporation of substantially all of the solvent
(and a portion of the flashing aids, if employed), to a temperature
below the softening temperature of the polymer, preferably below
about 100.degree.C.
In a typical flashing procedure in accordance with this invention
vaporization may be substantially complete 10 to 100 cm downstream
of the nozzle. However, this can vary widely depending on the flow
velocity, flash zone pressure, flash temperature, solvent, etc.
Importantly, in the mixture to be flashed, all of the components of
the mixture and the concentration of each in the mixtures are
chosen with respect to the heat capacity of each, with respect to
the heat vaporization of each component which will be volatized in
flashing, and with respect to the flash temperature chosen so as to
produce in the flashed product a temperature above the boiling
point of the solvent but preferably less than about 100.degree.C
upon flashing of the mixture into the flash zone. Expressed in
another way, the heat content of the mixture to be flashed and the
heat to be removed through vaporization of the vaporizable
components (solvent and any flashing aids vaporized, if employed)
should be adjusted so that the residual heat in the flashed
product, after removal of the heat of vaporization of the vaporized
components, will impart a temperature in the flashed product which
is between the boiling point of the solvent and about 100.degree.C.
Selection of the appropriate flashing temperature and of the
components of the mixture and their concentrations for this purpose
will depend upon the pressure selected for the flash zone and the
amount of heat added to the flash material during flashing if the
flashing is performed non-adiabatically. Preferably the flash zone
is at substantially atmospheric pressure. However, it can be at
subatmospheric pressure, (i.e., below about 600 mm Hg) as disclosed
in copending application Ser. No. 340140. If the flash temperature
is too high or if the components of the flash mixture and their
concentrations with respect to their heat capacity and heat of
vaporization (for the vaporizable components) are improperly
chosen, the temperature of the flashed product, upon substantially
complete evaporation of the solvent, will remain above
100.degree.C. If the flash temperature is too low, or, again, the
components are improperly chosen with respect to heat capacity and
heat of vaporization, there will be incomplete evaporation of the
solvent. For the purpose of this invention appropriate selection of
these variable parameter, namely, the flash temperature, components
and concentrations thereof in the flash mixture, may be determined
for a given pressure condition in the flash zone by making a heat
balance for the flashing operation which will produce the desired
noodle temperature below 100.degree.C. Advantageously, these
variable parameters may be selected so as to satisfy the following
equation: ##EQU1## Q.sub.p = Enthalpy of polymer(s) in flash
mixture Q.sub.s = Enthalpy of solvent(s) in flash mixture
Q.sub.f = Enthalpy of flashing aid(s) in flash mixture
Q.sub.na = Heat added to flashing mixture (if non-adiabatic)
V.sub.s = Enthalpy of vaporization of solvent vaporized
V.sub.f = Enthalpy of vaporization of flashing aids vaporized (if
any).
W.sub.p = Weight of polymer in the flashed product
C'.sub.p = Heat capacity of polymer in flashed product
W'.sub.f = Weight respectively, of the flashing aids, adjuvants,
and/or non-volatile components other than polymer in the flashed
product (if any).
C'.sub.f = Heat capacity of the respective flashing aids,
adjuvants, and/or non-volatile components other than polymer in the
flashed product (if any).
T.sub.b.p. = Boiling temperature of the solvent at the flash zone
pressure.
and where such enthalpy values are basaed on the same temperature
datum plane and the heat capacities are those applicable between
such datum plane and the temperature of the flashed product.
In using this formula, the heat capacity values and weights of the
flash components may be substituted into this formula, for example,
as follows for the specific case where a single polymer, solvent
and flashing aid are present in the flash mixture: ##EQU2## where
the additional terms are: W.sub.s = Weight of the solvent in the
flash mixture
C.sub.s = Heat capacity of the solvent in the flash mixture
W.sub.f = Weight of the flashing aid in the flash mixture
C.sub.f = Heat capacity of the flashing aid in the flash
mixture
C.sub.p = Heat capacity of the polymer in the flash mixture
H.sub.f = Heat of vaporization of solvent under flash
conditions.
H.sub.s = Heat of vaporization of flashing aids under flash
conditions.
T.sub.f = Flash temperature, .degree.C
and where the indicated heat capacities are those applicable
between the flash temperature and the previously mentioned
temperature datum plane.
In practice, the heat capacity and enthalpy of vaporization values
for the desired components can be substituted into this equation.
Then, a flash temperature and the concentrations of the flash
mixture components may be selected relative to each other to
satisfy the equation for a desired flashed product temperature. For
ease of calculation it can be useful to program these variables for
computer analysis to select the desired components and flash
temperature.
It is not necessary to actually measure the noodle temperature
(which is a cumbersome procedure under the flash zone conditions).
All that is necessary for control purposes is to maintain the
indicated parameters for the flash procedure at values that satisfy
this equation for the noodle temperature to be above the boiling
point of the solvent but below 100.degree.C. Of course, the various
parameters should also satisfy the other conditions for proper
flashing as previously discussed, e.g., the flash temperature
should be above the melt dissolution temperature, substantially all
of the solvent should be vaporized, etc.
During flashing, the polymer is precipitated as a fibrous product
or "noodle", which is a loose aggregation of fibers which is
sometimes continuous. The fibrous product is collected in a
suitable receiving vessel, preferably one which permits the
vaporized solvent to be separated therefrom.
The fibrous product in the receiving vessel may be either
substantially "dry" as flashed from a polyolefin solution or as an
aqueous slurry if flashed from a dispersion or emulsion employing
water as a flashing aid. However, in both cases a certain amount of
unflashed residual solvent will remain with the fibrous product
which can be subsequently removed.
In the copending application Ser. No. 340140 of H. Yonemori
referred to above, it was discovered that improved products were
obtained by refining the fibrous product at relatively low
temperatures, and to promote continued vaporization of the solvent
the vapor separation zone and the refining zone had to be
maintained under subatmospheric pressure.
The present invention resides in the discovery that similarly
improved products can be obtained by carrying out the refining of
the cooled fibrous product while it is maintained at substantially
atmospheric pressure, i.e., a pressure between about 600 and 800 mm
Hg.
The fibrous product is cooled to a temperature between about
10.degree.C and 60.degree.C prior to subjecting it to primary
refining it at substantially atmospheric pressure. If the
temperature employed is higher than about 60.degree.C, the drainage
factor of the pulp is detrimentally effected. Temperatures below
about 10.degree.C do not give any substantial improvement and
become uneconomical to use. Preferably the temperature is between
10.degree. and 40.degree.C.
The manner in which the fibrous product is cooled is not critical.
The fibrous product can be produced at the proper temperature by
employing a flashing zone at subatmospheric pressure (as described
in copending application Ser. No. 340140) or by employing a low
boiling solvent, i.e. one having a boiling point less than about
60.degree.C, or by a combination of a subatmospheric pressure flash
zone and low boiling solvent.
Alternativey, the fibrous product can be produced at an elevated
temperature up to about 100.degree.C, and cooled to the appropriate
temperature by use of cold dilution water, external cooling means,
or a combination of these or other conventional cooling
methods.
Prior to passing the fibrous product through such primary refining
zone, dilution water is added in the receiving vessel to provide an
aqueous slurry of the fibrous product having an appropriate
consistency. Typically, the consistency of the squeous slurry is
between about 1 to 10% by weight of the fibrous material although
high consistencies between about 10% and 60% by weight may be
employed by using screw feeding or similar feeding means. The
dilution water temperature should desirably be such as to provide
an aqueous slurry having a temperature between about 15.degree.C
and 40.degree.C, although external cooling can be employed to lower
the slurry temperature to within this range.
The aqueous slurry of fibrous product at the appropriate
consistency and temperature is then passed through the primary
refining zone to effect the desired vigorous fibrillating action on
the material. In its preferred form, the primary refining zone is a
disc refiner of the type conventionally employed in the papermaking
art and may employ either a single or double rotating disc. The
refiner is operated to impart a vigorous fibrillating action to the
fibrous product passing therethrough. This is accomplished by
spacing the discs relatively close together, that is, by a distance
between about 0 and 2500 microns, preferably between about 0 and
200 microns. The moving disc or discs are rotated at speeds to
provide relative peripheral velocities between about 4000 and 8000
feet per minute. The size of the discs and the plate design may be
any of those normally employed in the papermaking art. The primary
refining may be carried out by passing the fibrous material one or
more times through the refining zone. The "vigorous fibrillating"
action may be characterized by the amount of work done on the
fibers in the primary refining zone. The work imparted to the
fibrous product passing through the primary refining zone is
desirably greater than about 0.2 Kilowatt-hour/Kilogram.
The refining action just described may also be characterized by the
fiber fractionation as carried out in accordance with TAPPI
Standard Test T.-233- SU64, wherein 0.5% by weight of the fiber in
an aqueous slurry is fractionated for 20 minutes in a Bauer-McNett
classifier equipped with 20, 35, 65, 150 and 270 Tyler mesh
screens. After refining, the amount of fiber left on the 20 plus 35
mesh Tyler screens should be less than 90% by weight and preferably
less than about 60% by weight of the sample.
The aqueous slurry of fibrous product reslting from the primary
refining operation drops from the bottom of the disc refiner into a
receiving vessel which may be purged with an inert gas such as
nitrogen to remove any solvent vaporized during the primary
refining step.
The resulting pulp may be subjected to further or "secondary"
refining if desired.
By employing the refining sequence just described, i.e., primary
refining of the fibrous material as a reduced temperature a pulp is
produced having superior qualities. In this respect, one indication
of the improvement of the fibers made by the process of the present
invention is the drainage factor of such fibers as compared to
fibers of similar classified fiber length which are made using
parameters outside the present invention. The drainage factor is a
measure of the drainage characteristics of a fiber when a slurry
thereof is placed on a foraminous surfce. For synthetic fibers of
similar fiber length made by the flashing process, important
strength properties thereof correlate generally with their drainage
factor. For a fiber pulp having the same classified fiber length,
various strength properties of paper made therefrom increase with
the drainage factor of such fibers.
Another indication of improvement of the fibers made in accordance
with this invention is their slenderness relative to fibers
prepared by typical conventional technique. It is desirable to
produce fibers which are relatively thin (or of low coarseness) as
these fibers will impart higher capcity, density and better
formation to the paper prepared therefrom.
Generally, the set of operating parameters of the present invention
will result in improved fiber properaties such as thinness and
drainage factor compared with fibers prepared using typical
conventional parameters. Because other process variables in
addition to the specific parameters of this invention also
influence fiber properties (e.g., flash nozzle size and
configuration, polymer type and molecular weight, solvent, flashing
aids, dispersants, etc.), such resulting fiber comparasons are
appropriately made with the other process variables held
constant.
For the same reason, i.e., the influence of other process
conditions besides the parameters specific to this invention on the
resulting fiber properties, no absolute fiber property values can
be assigned to the fibers which may be prepared by the process of
this invention. However, with appropriate selection of all
parameters, it has been found that pulps can be produced in
accordance with this invention which have a drainage factor in
excess of 1 often in excess of 10 and as high as 100 to 200 seconds
per gram or higher and which have an average coarseness below about
15 decigrex (m/100 m). For papermaking use, a drainage factor
between 2 and 10 may be the preferred range as an appropriate
balance between increased strength and ease of water removal from
the fibers. Higher drainage factors can be obtained and may be
useful where the enhanced strength is more important than rapid
water removal.
In the accompanying drawing,
FIG. 1 represents a schematic representation of apparaus suitable
for use in carrying out the process of this invention, and
FIG. 2 is a detailed representation of the flash nozzle
schematically. shown in FIG. 1.
In FIG. 1, 1 is a steam jacketed vessel, provided with an agitator
1a, which may be charged with solvent, polymer (or polymer
solution) and, if desired, flashing aids such as water. Conduit 2
is provided at the bottom of the vessel 1 in communication with
flash nozzle 3 through shut-off valve 4 (preferably a ball valve).
As seen in FIG. 2, flash nozzle 3 has a substantially smaller
diameter than conduit 2. After the mixture is heated to the desired
temperature and agitated, if necessary, to dissolve the polymer
and/or disperse the flashing aids, valve 4 is opened and the
mixture thus formed is forwarded from vessel 1 through flashing
nozzle 3 under autogenous pressure of the heated mixture. As the
mixture discharged from vessel 1, nitrogen or other inert gas may
be introduced into the head space thereof through line 5 in order
to maintain the pressure in the vessel at autogenous or higher
pressure. The mixture is flashed through nozzle 3 into the flash
zone which is comprised of a vapor separation vessel such as
cyclone 6, and connecting conduit 7. Conduit 7 is a pipe having an
internal cross-sectional area larger than that of flash nozzle 3
and of sufficient internal diameter to permit rapid, unrestricted
passage of the flashed noodle to cyclone 6 and preferably has an
internal cross-sectional area many times larger than that of the
nozzle 3. Optionally, low pressure steam may be introduced into
conduit 7 through line 8 located shortly beyond flash nozzle 3 to
aid in the vaporization of solvent from the precipitated
noodle.
Vaporized solvent and water leaving cyclone 6 pass through line 21
to a solvent recovery unit (not shown).
The flashed fibrous noodle entering cyclone 6 through conduit 7,
together with the unvaporized portion of water or other flashing
aid present, passes downward through conduit 9 into primary disc
refiner 10. Conduit 11 is provided for introduction of dilution
water at an appropriate temperature to form a mixture or slurry
with the fibrous material having an appropriate temperature and
consistency for disc refining.
The material leaving the primary refiner 10 passes through conduit
12 to first receiving rank 13. Nitrogen is introduced into tank 13
through line 14 which sweeps out solvent vapors which are removed
via suitable means not shown.
The slurry may be withdrawn from receiving tank 13 through line 15
utilizing pump 16, for secondary refining in disc refiner 17. The
fibrous slurry leaving secondary refiner 17 passes through conduit
18 to second receiving tank 19 where it is collected prior to
further processing for shipment or for papermaking use. If desired,
the fibrous slurry leaving refiner 17 may be recycled through line
20 for one or more additional passes through refiner 17.
The fibers after refining may be diluted to a suitable consistency
and made into synthetic paper webs either alone or blended with
normal cellulose papermaking fibers. Alternatively, the fibers can
be dewatered, pressed into bales, stored and shipped to the
ultimate user.
The illustrated apparatus may be operated on a batch basis as
described or on a continuous basis by continuously feeding vessel 1
with polymer solution and any flashing aids desired at flow rates
to maintain the appropriate mixture in the vessel for flashing,
while heating the vessel to maintain the mixture at the appropriate
flash temperature. In order to insure uniform dispersion of
flashing aids, it may be desirable to place an in-line mixing
device in line 2 between vessel 1 and flash nozzle 3.
Optionally, instead of using a stirred heated vessel such as vessel
1, it is also possible to prepare the mixture on a continuous basis
by blending a polymer solution with any flashing aids desired (as
by adding superheated water) continuously in an in-line mixing
device just prior to flashing through a nozzle. It is also possible
to utilize an in-line mixer.
The following examples will illustrate the invention.
EXAMPLE 1
The apparatus employed in this example is that illustrated in the
drawing and previously described. The dissolution vessel 1 was a 2
gallon stirred autoclave equipped with five 4 inch impellers on a
single shaft rotated at 1000 r.p.m.
The vessel was charged with 0.32 Kg of polyethylene (Mitsui 2200P)
having an intrinsic viscosity ( .eta.) of 1.4 dl/gram. 4 liters of
n-hexane, 4 liters of water and 2% by weight of 88% hydrolyzed
polyvinyl alcohol (Gelvatol 20/30 made by Monsanto) based on the
polyethylene. The vessel was sealed and the contents raised to a
temperature of 145.degree.C .+-. 2.5.degree.C. The vessel was
pressurized with nitrogen to a pressure of 160 psig. The heated
contents were then flashed through a nozzle 3 having a diameter of
2.5 mm and a length of 28.5 mm into a receiving vessel 6. Dilution
water at a temperature of 93.degree.C was added to the fibrous
material to provide a slurry having a cosistency of about 1% by
weight. The aqueous fibrous slurry at a temperature of about
40.degree.C was then passed through a primary refining zone
consisting of a Sprout Waldron single moving disc refiner having 12
inch plates (Pattern C29 -79B) at a plate clearance of 0.005 inch.
The peripheral velocity of the refiner disc was 5495 feet per
minute (1750 r.p.m.). The resulting pulp had a drainage factor of
12.6 seconds/gram, a surface area (gas adsorption) of 12.7 m.sup.2
/gram, and a fiber fraction on the 20 plus 35 mesh screen of 16%.
Handsheets were made from the pulp in accordance with TAPPI
Standard Test T-205M-58, with modified wet processing (400 psig)
and a heat bonding treatment (121.degree.C at minimum pressure).
The handsheets were tested and had the following properties:
Basis weight, g/m.sup.2 60.5 Tensile, Kg/15 mm 1.19 Breaking
length, m 1309 Tensile Energy Absorption, Kg-cm/cm.sup.2 0.037
Scott Internal Bond, Kg-cm/cm.sup.2 .times. 10.sup.-.sup.3 155
Opacity, % TAPPI corrected) 96.8
Handsheets were also prepared by blending the above-described
polyethylene fibers 50/50 with bleached alder kraft pulp having a
Canadian Standard Freeness of 150 c.c. The properties of the
resulting handsheets were as follows:
Basis weight, g/m.sup.2 59.9 Tensile, Kg/15 mm 2.40 Breaking
length, m 2677 Tensile Energy Absorption Kg - cm/cm.sup.2 0.032
Scott Internal Bond C, Kg-cm/cm.sup.2 .times. 10.sup.-.sup.3 319
Opacity, % (TAPPI corrected) 94.6
In the foregoing example and subsequent examples, the sheet
density, basis weight and caliper were determined by TAPPI Standard
T-220, tear strength by TAPPI Standard T-414, opacity by TAPPI
Standard T-425 m-60, coarseness by TAPPI Standard T-234 SU 67, and
tensile strength, stretch, tensile energy adsorption and breaking
length were determined by TAPPI Standard T-494.
The Scott Internal Bond was determined by employing the Scott
instrument under the standard procedure.
The drainage factor in this and following examples was 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 is 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: ##EQU3## 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.
COMPARATIVE EXAMPLE 1
In order to show the improvement in fiber properties obtained by
subjecting the fibrous noodle to a rigorous fibrillating action at
a reduced temperature, example 1 was repeated except that the
primary refining was accomplished by passing the fibrous noodle at
a temperature of 93.degree.C through the refiner with the plates
set at 0.005 inch apart. The resulting pulp had a drainage factor
of 0.17 seconds/ gram. The resulting pulp was then cooled to about
40.degree.C as in example 1 and passed once through a secondary
refiner having a plate clearance of 0.005 inch. The resulting pulp
had a drainage factor of only 0.57 seconds/gram compared to 12.6
seconds/gram for the pulp of example 1. The lower drainage factor
is indicative of a fiber which will form a much weaker sheet.
EXAMPLE 2
Example 1 was repeated except that the polyvinyl alcohol was
present in the amount of 5 % by weight of the polyethylene. It took
76 seconds to pass all the material through the nozzle. After
cooling to about 40.degree.C and one pass primary refining at a
plate clearance of 0.005 inch the resulting pulp had a drainage
factor of 108 seconds/gram, a surface area of 14.4 m.sup.2 /gram
and a fiber fraction on the 20 plus 35 mech screens of 55% by
weight. This example illustrates that increasing the amount of
polyvinyl alcohol during refining further enhances the drainage
factor of the resulting pulp. Handsheets (both 100% and a 50/50
blend) were prepared as in example 1. The properties were as
follows:
Property 100% 50/50 ______________________________________ Basis
weight g/m.sup.2 61.5 60.2 Tensile, Kg/15 mm 1.83 3.0 Breaking
length, m 1991 3321 Tensile Energy Absorption, Kg-cm/cm.sup.2 0.359
0.061 Scott Internal Bond Kg-cm/cm.sup.2 (.times. 10.sup.-3) 304
352 Opacity % (TAPPI corrected) 96.1 93.1
______________________________________
EXAMPLE 3
Example 1 was repeated except that the temperature of the contents
of the dissolution vessel was 149.degree.C, and low pressure steam
(10 psig) was introduced into line 7 via line 8 which entered line
7 3 inches downstream of nozzle 3. Two different kinds of polyvinyl
alcohol were employed. In the first run, the polyvinyl alcohol
employed was Hoechst Movial 30-88 which is 88% hydrolyzed and has a
viscosity (4% by weight aqueous solution at 20.degree.C) of 3-5
centipoises and in the second run the polyvinyl alcohol was Hoechst
30-98 which is 98% hydolysed and has a viscosity of 3-5
centipoises. Primary refining was effected at a temperature of
40.degree.C and a plate clearance of 0.005 inch.
The resulting pulps had the following properties:
Run PVA Drainage Factor Classified No. % Hydrolyzed sec/g. Fiber
length, mm ______________________________________ 1 88 14.1 1.15 2
98 5.0 1.09 ______________________________________
Handsheets made from the pulps, both 100% and 50/50 blends with
bleached alder kraft, as in example 1. The handhseet properties
were:
Property 100% Handsheets 50/50 Handsheets PVA % Hydrolysis PVA %
Hydrolysis 88% 98% 88% 98% ______________________________________
Basis weight g/m.sup.2 63.3 62.5 58.5 57.4 Caliper, mm 0.15 0.16
0.11 0.11 Density, g/cc 0.41 0.40 0.53 0.52 Tear, g/sheet 35.2 25.6
35.2 32.2 Tensile, Kg/15 mm 1.2 0.97 2.6 2.3 Breaking length, m
1.26 1.04 2.98 2.68 Stretch % 7.1 5.6 3.7 3.2 Tensile Energy
Absorption, Kg-cm/cm.sup.2 0.05 0.03 0.05 0.03 Scott Internal Bond
cm/cm.sup.2 .times.(10.sup.-.sup.3) 175 200 184 183 Opacity, %
(TAPPI corrected) 97.6 96.6 94.7 92.6
______________________________________
This example illustrates that improved strength properties may be
obtained with the present process by employing polyvinyl alcohols
of various degrees hydrolysis, hydrlysis, and that the less
hydrolyzed polyvinyl alcohols are preferable.
EXAMPLE 4
Example 3 was repeated using polyvinyl alcohols having higher
molecular weights. The polyvinyl alcohol employed in run 1 was
Hoechst Movia 1 75-88 (viscosity of 20-25 centipoises) in 4%
aqueous solution at 20.degree.C, and is 88% hydrolyzed, and the
polyvinyl alcohol employed in run 2 was Hoechst Movial 75-98
(viscosity of 25-30 centipoises and is 98% hydrolyzed). The primary
refining was effected at a temperature of 40.degree.C and at a
plate clearance of 0.005 inch. The resulting pulps had the
following properties:
Run PVA % Drainage Factor Classified Fiber No. Hydrolyzed sec/g.
length, mm ______________________________________ 1 88 4.9 1.03 2
98 3.3 1.08 ______________________________________
Handsheets made from the pulps, both 100% and 50/50 blends with
bleached alder kraft, as in example 1 The handsheet properties
were:
Property 100% Handsheets 50/50 Handsheets PVA % Hydrolysis PVA %
Hydrolysis 88% 98% 88% 98% ______________________________________
Basis weight g/m.sup.2 60.4 58.6 60.2 58.7 Caliper, mm 0.16 0.15
0.12 0.11 Density, g/cc 0.38 0.37 0.51 0.53 Tear, g/sheet 22.4 12.8
32 32 Tensile, Kg/15 mm 0.87 0.68 2.7 2.5 Breaking length, m 0.96
0.77 3.01 2.84 Stretch, % 7.0 2.6 3.4 3.3 Tensile Energy Absorption
Kg-cm/cm.sup.2 0.03 0.008 0.04 0.04 Scott Internal Bond cm/cm.sup.2
.times. (10.sup.-.sup.3) 183 120 249 164 Opacity, % (TAPPI
corrected) 97.7 96.9 93.7 93.1
______________________________________
This example illustrates that improved strength properties may be
obtained with the present process with polyvinyl alcohols of
varying molecular weights.
EXAMPLE 5
The apparatus employed in this example is that illustrated in the
drawing and previously described except that ball valve 4 and
nozzle 3 were replaced with a valtek angle central valve with a 9.5
mm diameter orifice. The dissolution vessel 1 was an 800 gallon
stirred autoclave.
The stirred vessel was charged with 300 gallons of hexane, 91 Kg of
polyethylene (Mitsui 2200P) having an intrinsic viscosity (.eta.)
of 1.4 dl/gram, and 60 gallons of water and 3% by weight of 88%
hydrolyzed polyvinyl alcohol (Gelvatol 20/30 made by Monsanto)
based on the polyethylene (2730 grams). The vessel was sealed and
the contents raised to a temperature of 140.degree.C. The heated
contents were then flashed through the control valve into receiving
vessel 6 at a rate of about 200-250 grams polyethylene per minute.
Low pressure (10 psig) steam was introduced into line 7 via line 8
located about 6 inches downstream of the control valve. Dilution
water at a temperature of 85.degree.C was added to the fibrous
material at a rate of about 51/2 gallons/minute. Part of the
aqueous fibrous slurry at a consistency of 1 % and at a temperature
of 85.degree.C was then passed through a primary refining zone
consisting of a Jones double disc refiner having 12 inch plates
(Pattern 1,1,1,1/2 + 10.degree.) at a plate clearance of 0.002 inch
(0.05 mm). The peripheral velocity of the moving refiner disc was
6688 feet per minute (2130 r.p.m.).
The slurry was passed through the refiner at a flow rate of about
15 liters per minute. A second portion of the fibrous material was
collected and cooled to a temperature of about 20.degree.C prior to
refining, and was then subjected to primary refining under the same
conditions as the first sample. Both samples were subjected to five
passes of secondary refining at 20.degree.C, the other refining
conditions being the same as for the primary refining. Handsheets
(both 100% and 50/50 blends) were made and tested as in example 1.
The fiber and handsheet properties were as follows:
Property Run 1 Run 2 85.degree.C Primary 20.degree.C Primary
Refining. Refining ______________________________________ Drainage
factor sec/g. 18.4 114.1 Fiber Fractionation % on 20 mesh screen
2.3 6.7 35 mesh screen 38.2 25.4 65 mesh screen 23.5 28.2 150 mesh
screen 17.7 20.1 270 mesh screen 5.2 10.7 Trhough 13.1 8.9
Classified fiber Length 1.01 0.97 100% Handsheet Density, g/cc 0.44
0.44 Corr. Opacity % 96.7 95.8 Scattering Coefficient cm.sup.2 /g
90.8 91.7 Brightness % 90.8 91.7 Breaking length 1154 1855 TEA,
kg-cm/cm.sup.2 0.052 0.163 Internal Bond, Scott units 64 167 Tear,
g/sheet 19 32 Basis weight, g/m.sup.2 59.9 62.2 50/50 Handsheet
Density g/cc 0.58 0.57 Corr. Opacity % 91.2 91.5 Scattering
Coefficient cm.sup.2 /g 744 763 Brightness, % 85.1 86.0 Breaking
length, m 3332 3545 TEA, kg-cm/cm.sup.2 0.051 0.066 Internal Bond,
Scott Units 119 162 Tear g/sheet 30 33 Basis weight g/m.sup.2 61.2
63.1 ______________________________________
This example clearly shows the marked improvement of properties,
such as drainage factor, obtained by employing the cold primary
refining concept of the present invention.
* * * * *