U.S. patent number 3,619,453 [Application Number 04/873,670] was granted by the patent office on 1971-11-09 for wet spinning process for the production of polybenzimidazole filaments.
This patent grant is currently assigned to Celanese Corporation. Invention is credited to John P. Riggs.
United States Patent |
3,619,453 |
Riggs |
November 9, 1971 |
**Please see images for:
( Certificate of Correction ) ** |
WET SPINNING PROCESS FOR THE PRODUCTION OF POLYBENZIMIDAZOLE
FILAMENTS
Abstract
An improved wet spinning process is provided which is capable of
producing highly uniform polybenzimidazole filaments which are
substantially free of internal voids and radial incursions. A
solution of the polybenzimidazole is extruded into a coagulation
bath of certain polyhydroxy aliphatic alcohols to form an as-spun
filament which is at least initially washed in a relatively cool
wash medium, followed by drying, and stretching. The uniform
filaments formed in the process are useful as precursors in the
formation of carbon or graphite fibrous materials or as a substrate
for metal deposition. When heavy denier filaments are formed in in
the present process, these are particularly suited for use in the
formation of fibrous closures.
Inventors: |
Riggs; John P. (Berkely
Heights, NJ) |
Assignee: |
Celanese Corporation (New York,
NY)
|
Family
ID: |
25362100 |
Appl.
No.: |
04/873,670 |
Filed: |
November 3, 1969 |
Current U.S.
Class: |
264/184;
264/210.1; 264/235; 264/344; 264/203; 264/233 |
Current CPC
Class: |
D01F
6/74 (20130101); D01F 9/24 (20130101) |
Current International
Class: |
D01F
9/14 (20060101); D01F 6/58 (20060101); D01F
6/76 (20060101); D01F 9/24 (20060101); D01d
005/06 () |
Field of
Search: |
;264/184,203,210,233,235,344,182,290 ;260/47CZ,47CP,78TF,78S |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Frome; Julius
Assistant Examiner: Mintz; Herbert
Claims
I claim:
1. An improved wet spinning process for the production of
polybenzimidazole filaments comprising:
a. providing a spinning solution of a fiber-forming
polybenzimidazole dissolved in a solvent selected from the group
consisting of dimethylacetamide, N,N-dimethylformamide, dimethyl
sulfoxide, and N-methyl-2-pyrrolidone,
b. extruding said spinning solution into a coagulation bath having
a temperature of about 30.degree. to 100.degree. C. selected from
the group consisting of a polyhydroxy hydrocarbon alcohol having 2
to 3 hydroxy groups and 2 to 6 carbon atoms, mixtures of said
polyhydroxy hydrocarbon alcohols, at least one of said polyhydroxy
hydrocarbon alcohols in admixture with up to about 70 percent water
by weight based upon the total weight of the mixture, and a least
one of said polyhydroxy hydrocarbon alcohols in admixture with up
to about 50 per cent by weight of at least one of said solvents
based upon the total weight of the mixture,
c. washing the resulting as-spun filament in water until
substantially all residual amounts of said solvent and said
coagulation bath are removed from said filament with said washing
being initially conducted for at least 25 seconds with said water
at a temperature of about 5.degree. to 25.degree. C.,
d. drying said washed filament, and
e. heating said dried filament at a temperature of about
450.degree. to 600.degree. C. while simultaneously stretching said
filament about 1.5 to 10 times its original length.
2. An improved process according to claim 1 which includes the
additional step of relaxing said stretched filament at a
temperature of about 350.degree. to 525.degree. C.
3. An improved process according to claim 1 wherein said
fiber-forming polybenzimidazole consists essentially of recurring
units of the formula: ##SPC4##
wherein R is a tetravalent aromatic nucleus, with the nitrogen
atoms forming the benzimidazole rings paired upon adjacent carbon
atoms of said aromatic nucleus, and R' is selected from the group
consisting of (1) an aromatic ring, (2) an alkylene group having
from four to eight carbon atoms, and (3) a heterocyclic ring
selected from the group consisting of (a) pyridine, (b) pyrazine,
(c) furan, (d) quinoline, (e) thiophene, and (f) pyran.
4. An improved process according to claim 1 wherein said
polybenzimidazole is poly 2,2' -(m-phenylene)-5,5'
-bibenzimidazole.
5. An improved process according to claim 1 wherein said solvent
utilized in the formation of said spinning solution is
dimethylacetamide.
6. An improved process according to claim 1 wherein said spinning
solution contains 20 to 30 percent by weight based upon the total
weight of the solution of poly
2,2'-(m-phenylene)-5,5'-bibenzimidazole dissolved in
dimethylacetamide.
7. An improved process according to claim 1 wherein said
coagulation bath has a temperature of about 30.degree. to
60.degree. C.
8. An improved process according to claim 1 wherein said
coagulation bath is ethylene glycol.
9. An improved process according to claim 1 wherein said
coagulation bath is glycerol.
10. An improved process according to claim 5 wherein said
coagulation bath is a mixture of ethylene glycol and
dimethylacetamide containing up to about 20 percent by weight
dimethylacetamide based upon the total weight of said mixture.
11. An improved process according to claim 1 wherein said
coagulation bath is a mixture of glycerol and water containing up
to about 40 percent by weight water based upon the total weight of
said mixture.
12. An improved process according to claim 1 wherein said resulting
as-spun filament is initially washed in water at a temperature of
about 10.degree. to 15.degree. C.
13. An improved process for the production of a polybenzimidazole
filament comprising:
a. providing a spinning solution of poly 2,2'-(m-phenylene)-5,5'
-bibenzimidazole dissolved in dimethylacetamide in a concentration
of about 20 to 24 percent by weight based upon the total weight of
the solution,
b. extruding said spinning solution into an ethylene glycol
coagulation bath having a temperature of about 30.degree. to
60.degree. C.,
c. initially washing the resulting as-spun filament for at least 25
seconds in water at a temperature of about 5.degree. to 25.degree.
C.,
d. subsequently washing the filament in water at a temperature of
about 30.degree. to 100.degree. C. until substantially all residual
amounts of dimethylacetamide and ethylene glycol are removed from
said filament,
e. drying said washed filament, and
f. heating said dried filament at a temperature of about
450.degree. to 600.degree. C. while simultaneously stretching said
filament about 1.5 to 10 times its original length.
14. An improved process according to claim 13 which includes the
additional step of relaxing said stretched filament about 10 to 65
percent in length at a temperature of about 350.degree. to
525.degree. C.
15. An improved process according to claim 13 in which said step(e)
is conducted at about 475.degree. to 500.degree. C. while
simultaneously stretching said filament about 2.5 to 3.5 times its
original length.
Description
BACKGROUND OF THE INVENTION
Polybenzimidazoles are a known class of heterocyclic polymers which
are characterized by a high degree of thermal stability. These
polymers are described, for instance, in U.S. Pat. No. 2,895,948 to
Brinker et al and in U.S. Reissue Pat. No. 26,065 to Marvel et al.
Polybenzimidazole fibers are recognized to exhibit great resistance
to degradation by heat, hydrolytic media, and oxidizing media.
Polybenzimidazole fibers of relatively low denier (e.g. from about
1 to about 10 denier per filament) have commonly been formed by
various dry spinning techniques in which the spinning solution is
extruded into a suitable evaporative medium to form fibers
exhibiting a dogbone cross section. Polybenzimidazole fibers of
essentially round cross sections are very rarely achieved through
dry spinning processes. It also has not been possible to produce
acceptable high denier (e.g. from about 50 to 2000 denier per
filament) polybenzimidazole filaments by dry spinning
techniques.
A process for the wet spinning of polybenzimidazole shaped articles
in which a spinning solution of the polymer in sulfuric acid is
extruded into a coagulation bath containing sulfuric acid at a
concentration lower than that of the spinning solution is disclosed
in U.S. Pat. No. 3,441,640 to Santangelo. Attempts to prepare an
acceptable high denier polybenzimidazole fiber by this method
failed because the filaments were too cracked and brittle.
Commonly assigned U.S. Pat. No. 3,526,693 of Richard N. Rulison and
John P. Riggs discloses a wet spinning process for the formation of
high denier polybenzimidazole filaments in which the resulting
round filament is subjected to a series of controlled thermal
healing treatments to heal radial incursions and to increase
tensile properties.
It is an object of the invention to provide an improved wet
spinning process for the formation of uniform as-spun
polybenzimidazole filaments without the need to practice a thermal
healing treatment to close voids and spin bath incursions.
It is an object of the invention to provide an efficient wet
spinning process for the formation of polybenzimidazole filaments
which possess smooth surface characteristics and are substantially
free of internal voids and radial incursions.
It is an object of the invention to provide an efficient wet
spinning process which in at least some of its embodiments is
capable of forming polybenzimidazole filaments which are
substantially round as well as substantially free of internal voids
and radial incursions.
It is an object of the invention to provide an improved process
which is particularly suited for the formation of uniform heavy
denier polybenzimidazole filaments which are suitable for use in
the manufacture of fibrous closures.
It is another object of the invention to provide essentially
homogenous wet spun polybenzimidazole filaments which are suitable
for use as precursors in the production of amorphous carbon or
graphite fibers.
It is a further object of the invention to provide essentially
homogenous wet spun polybenzimidazole filaments which are suitable
for use as substrates for metal deposition.
These and other objects, as well as the scope, nature, and
utilization of the invention will be apparent to those skilled in
the art from the following detailed description and appended
claims.
SUMMARY OF THE INVENTION
It has been found that an improved wet spinning process for the
production of uniform polybenzimidazole filaments comprises:
a. providing a spinning solution of a fiber-forming
polybenzimidazole dissolved in a solvent selected from the group
consisting of dimethylacetamide, N,N-dimethylformamide, dimethyl
sulfoxide, and N-methyl-2 -pyrrolidone,
b. extruding said spinning solution into a coagulation bath having
a temperature of about 30.degree. to 100 .degree. C. selected from
the group consisting of a polyhydroxy aliphatic alcohol having 2 to
3 hydroxy groups and 2 to 6 carbon atoms, mixtures of the
polyhydroxy aliphatic alcohols, at least one of the polyhydroxy
aliphatic alcohols in admixture with up to about 70 percent water
by weight based upon the total weight of the mixture, and at least
one of the polyhydroxy aliphatic alcohols in admixture with up to
about 50 percent by weight of at least one of the solvents based
upon the total weight of the mixture,
c. washing the resulting as-spun filament in water until
substantially all residual amounts of the solvent and the
coagulation bath are removed from the filament with the washing
being initially conducted for at least 25 seconds with water at a
temperature of about 5.degree. to 25.degree. C.,
d. drying the washed filament, and
e. heating the dried filament at a temperature of about 450.degree.
to 600.degree. C. while simultaneously stretching the filament
about 1.5 to 10 times its original length.
The resulting stretched filament may optionally be relaxed at a
temperature of about 350.degree. to 525.degree. C.
DETAILED DESCRIPTION OF THE INVENTION
The Starting Polymer
The polybenzimidazoles which are wet spun according to the present
process are the fiber-forming (fiber-formable) linear
polybenzimidazoles. Typical polymers of this class and their
preparation are more fully described in U.S. Pat. No. 2,895,948,
U.S. Reissue Pat. No. 26,065, and in the Journal of Polymer
Science, Vol. 50, pages 511- 539 (1961 ) which are herein
incorporated by reference. The polybenzimidazoles consist
essentially of recurring units of the following formulas I and
II.
Formula I is: ##SPC1##
wherein R is a tetravalent aromatic nucleus, preferably
symmetrically substituted, with the nitrogen atoms forming the
benzimidazole rings being paired upon adjacent carbon atoms, i.e.,
ortho carbon atoms, of the aromatic nucleus, and R' is a member of
the class consisting of (1 ) an aromatic ring, (2 ) an alkylene
group (preferably those having 4 to 8 carbon atoms), and (3 ) a
heterocyclic ring from the class consisting of (a) pyridine, (b)
pyrazine, (c) furan, (d) quinoline, (e) thiophene, and (f)
pyran.
Formula II is: ##SPC2##
wherein Z is an aromatic nucleus having the nitrogen atoms forming
the benzimidazole ring paired upon adjacent carbon atoms of the
aromatic nucleus.
Preferably, aromatic polybenzimidazole filaments are wet spun in
the present invention, that is, filaments are prepared from
polymers consisting essentially of the recurring units of formulas
I and II wherein R' is an aromatic ring or a heterocyclic ring.
As set forth in U.S. Reissue Pat. No. 26,065, the aromatic
polybenzimidazoles having the recurring units of formula II may be
prepared by self-condensing a trifunctional aromatic compound
containing only a single set of ortho disposed diamino substituents
and an aromatic, preferably phenyl, carboxylate ester substituent.
Exemplary of polymers of this type is poly-2,5(6)-benzimidazole
prepared by the autocondensation of phenyl- 3,4
-diaminobenzoate.
As also set forth in the above-mentioned patent, the aromatic
polybenzimidazoles having the recurring units of formula I may be
prepared by condensing an aromatic tetraamine compound containing a
pair of ortho diamino substituents on the aromatic nucleus with a
dicarboxyl compound selected from the class consisting of (a) the
diphenyl ester of an aromatic dicarboxylic acid, (b) the diphenyl
ester of a heterocyclic dicarboxylic acid wherein the carboxyl
groups are substituents upon carbon in a ring compound selected
from the class consisting of pyridine, pyrazine, furan, quinoline,
thiophene and pyran and (c) an anhydride of an aromatic
dicarboxylic acid.
Examples of polybenzimidazoles which have the recurring structure
of Formula I are as follows:
poly- 2,2' -(m-phenylene) 5,5' -bibenzimidazole;
poly- 2,2'-(pyridylene-3" ,5")-5,5'-bibenzimidazole;
poly- 2,2'-(furylene-2" ,5" )-5,5'-bibenzimidazole;
poly- 2,2'-(naphthalene-1",6")- 5,5'-bibenzimidazole;
poly- 2,2'-(biphenylene 4",4"' )- 5,5'-bibenzimidazole;
poly-2, 2'-amylene- 5, 5'-bibenzimidazole;
poly-2, 2'-ocatmethylene-5, 5'-bibenzimidazole;
poly-2, 6 -(m-phenylene)-diimidazobenzene;
poly-2, 2'-cyclohexeneyl-5, 5'-bibenzimidazole;
poly-2, 2'-(m-phenylene)-5, 5'-di(benzimidazole) ether;
poly-2, 2'-(m-phenylene)-5, 5'-di(benzimidazole) sulfide;
poly-2, 2' -(m-phenylene)-5, 5'-di(benzimidazole) sulfone;
poly-2, 2' -(m-phenylene)-5, 5'-di(benzimidazole) methane;
poly-2', 2" -(m-phenylene)-5', 5" -di(benzimidazole) propane-2, 2;
and
poly-2", 2" -(m-phenylene)-5', 5" -di(benzimidazole) ethylene- 1,
2
where the double bonds of the ethylene groups are intact in the
final polymer.
The preferred polybenzimidazole for use in the present process is
one prepared from poly-2, 2'-(m-phenylene)-5, 5'-bibenzimidazole,
the recurring unit of which is: ##SPC3##
Any polymerization process known to those skilled in the art may be
employed to prepare the polybenzimidazole which is wet spun to form
a uniform filament in accordance with the process of the present
invention. With respect to aromatic polybenzimidazoles, preferably,
equimolar quantities of the monomeric tetraamine and dicarboxyl
compound may be introduced into a first stage melt polymerization
reaction zone and heated therein at a temperature above about
200.degree. C., preferably at least 250.degree. C., and more
preferably from about 270.degree. to 300.degree. C. The reaction is
conducted in a substantially oxygen-free atmosphere, i.e., below
about 20 p.p.m. oxygen and preferably below about 8 p.p.m. oxygen,
until a foamed prepolymer is formed. Usually, the first stage
reaction is continued until a prepolymer is formed having an
inherent viscosity, expressed as deciliters per gram, of at least
0.1, and preferably from about 0.13 to 0.3 (determined from a
solution of 0.4 grams of the polymer in 100 ml. of 97 percent
H.sub.2 SO.sub.4 at 25.degree. C.).
After the conclusion of the first stage reaction, which normally
takes at least 0.5 hours and preferably 1 to 3 hours, the foamed
prepolymer is cooled and then powdered or pulverized in any
convenient manner. The resulting prepolymer powder is then
introduced into a second stage polymerization reaction zone wherein
it is heated under substantially oxygen-free conditions, as
described above, to yield a polybenzimidazole polymer product,
desirably having an I.V., as measured above, of at least 0.6, e.g.
0.80 to 1.1 or more.
The temperature employed in the second stage is at least
250.degree. C., preferably at least 325.degree. C., and more
preferably from about 350.degree. to 425.degree. C. The second
stage reaction generally takes at least 0.5 hours, and preferably
from about 1 to 4 hours or more.
THE SPINNING SOLUTION
The spinning solution of the polybenzimidazole selected for use in
the present wet spinning process may be selected from those
solutions commonly used for the dry spinning of polybenzimidazole
filaments in accordance with the prior art. Solvents for the
polybenzimidazole suitable for use in the formation of the spinning
solution are dimethylacetamide, N,N-dimethylformamide, dimethyl
sulfoxide, and N-methyl-2-pyrrolidone. The particularly preferred
solvent is dimethylacetamide.
The polymer solutions may be prepared, for example, by dissolving
sufficient polybenzimidazole in the solvent to yield a final
solution suitable for extrusion containing from about 20 to 30
percent by weight of polymer, based on the total weight of the
solution, and preferably from about 20 to 24 per cent by weight.
The viscosity of the spinning solution should be within the range
of 500 to 8000 poise, and preferably in the range of about 1500 to
4000 poise at 30.degree. C.
One suitable means for dissolving the polymer in the solvent is by
mixing the materials at a temperature above the normal boiling
point of the solvent, for example, about 25.degree. to 120.degree.
C. above such boiling point, and at a pressure of 2 to 15
atmospheres for a period of 1 to 5 hours. The resulting solutions
are then filtered to remove any undissolved polymer which would
otherwise clog the spinning orifice. A minor amount of lithium
chloride optionally may be provided in the spinning solution in
accordance with the teachings of commonly assigned U.S. Pat. No.
3,502,606 of Anthony B. Conciatori and Charles L. Smart.
WET SPINNING
The spinning solution of fiber-forming polybenzimidazole is
extruded into a coagulation bath to form a filament having a smooth
surface which is substantially free of internal voids and radial
incursions. The homogeneous nature of the resulting as-spun
filament is preserved during the subsequent steps of the process
which further improve its usefulness.
It has been found that coagulation baths containing a substantial
quantity of polyhydroxy aliphatic alcohol having 2 to 3 hydroxy
groups and 2 to 6 carbon atoms are capable of producing highly
uniform filaments in the wet spinning process of the invention.
When used in combination with the subsequent steps of the process
the need for a thermal healing treatment to heal radial incursions
and to increase tensile properties as disclosed in U.S. Pat. No.
3,526,693 is totally obviated.
Representative polyhydroxy aliphatic alcohols of use in the present
process include glycols such as ethylene glycol [1,2 -ethanediol],
propylene glycol [1,2 -propanediol], trimethylene glycol [1,3
-propanediol], alpha-butylene glycol [1,2 -butanediol],
beta-butylene glycol [1,3 -butanediol], tetramethylene glycol [1,4
-butanediol] , sym-dimethylethylene glycol [2,3 -butanediol] ,
diethylene glycol [2,2' -oxydiethanol] , triethylene glycol [2,2'
-(ethylenedioxy)diethanol] , and hexamethylene glycol [1,6
-hexanediol]. Other polyhydroxy aliphatic alcohols such as glycerol
[1,2,3 -propanetriol] may likewise be selected. The particularly
preferred polyhydroxy aliphatic alcohol is ethylene glycol.
Filaments formed in the present process utilizing ethylene glycol
as the coagulation bath tend to be of a highly uniform round
configuration.
The coagulation bath may contain a single polyhydroxy aliphatic
alcohol, as defined, or a mixture of such alcohols. In another
embodiment of the process at least one of the polyhydroxy aliphatic
alcohols is present in admixture with up to about 70 per cent water
by weight based upon the total weight of the mixture, and
preferably not in excess of about 40 per cent water by weight, to
form the coagulation bath. Such coagulation baths which include
water have a tendency to increase the rate of coagulation.
Extremely rapid coagulation resulting from the use of a greater
proportion of water tends to result in the introduction of voids
and incursions into the resulting filaments. Alternatively, the
coagulation bath may contain a mixture of at least one of said
polyhydroxy alcohols with up to about 50 per cent by weight based
upon the total weight of the mixture of at least one of the
spinning solution solvents, and preferably not in excess of about
20 percent of at least one of the solvents. Such coagulation baths
containing an appreciable quantity of the solvent have a tendency
to decrease the rate of coagulation. If more than about 65 per cent
by weight of at least one of the solvents is present in the
coagulation bath, this results in little or no fiber formation at
practical spinning speeds depending upon the specific coagulation
bath.
The temperature of the spinning solution during the extrusion
should be within the range of 10.degree. to 180.degree. C. and
preferably at about 25.degree. to 80.degree. C. The spinneret
should contain holes of a diameter between about 40 to 150 microns
when producing relatively low denier filaments, and holes of about
200 to 600 microns when producing relatively high denier filaments.
Monofilaments or continuous multifilament yarns may be formed. The
extrusion pressure should be between 100 and 750 p.s.i. Spinning or
extrusion speeds of about 5 to 50 meters per minute, and preferably
about 10 to 20 meters per minute may be selected.
The coagulation bath containing at least one polyhydroxy aliphatic
alcohol into which the spinning solution is extruded is maintained
at a temperature of about 30.degree. to 100.degree. C., and
preferably at a temperature of about 30.degree. to 60.degree. C. If
the coagulation bath is maintained at a temperature much above
100.degree. C., then voids and incursions may result. If the
coagulation bath is maintained at a temperature much below
30.degree. C., then insufficient coagulation may result. The exact
temperature selected may be influenced by the extrusion speed, the
length of the coagulation bath, and the composition of the
coagulation bath.
The resulting as-spun filament is commonly present in the
coagulation bath for a residence time of about 1 to 15 seconds, and
preferably for a residence time of about 2 to 6 seconds.
WASHING AS-SPUN FILAMENT
The resulting as-spun filament is next washed with water until
substantially all residual amounts of solvent and coagulation bath
are removed from the same. It is essential that the filament first
be exposed to a relatively cool water wash medium at about
5.degree. to 25.degree. C., and preferably at a temperature of at
least about 10.degree. to 15.degree. C., for at least about 25
seconds. The entire wash treatment may be conducted at such
relatively cool temperature, or the water wash medium may be
subsequently raised to a more highly elevated temperature. The
initial cool water wash has been found to be essential in order to
preserve filament homogeneity.
When the entire wash is conducted at a relatively cool wash
temperature of about 5.degree. to 25.degree. C., wash times of
about 24 to 100 hours are commonly required depending upon the
filament denier.
During the cool water wash a one-way transfer of residual
quantities of the spinning solvent out of the filament is believed
to be promoted to the substantial exclusion of the passage of the
molecules of the wash medium into the filament. Such wash treatment
has been found to be highly important if the homogeneous nature of
the filament is to be preserved. For instance, it has been found
that if the as-spun filament is initially washed at a temperature
substantially higher than about 25.degree. C. then the resulting
washed fiber tends to lack homogeneity.
In a preferred embodiment of the invention, an initial cool water
wash step is followed by a subsequent wash step at a more highly
elevated temperature. For instance, the filament may be initially
water washed at a temperature of about 5.degree. to 25.degree. C.
for about 25 seconds to 5 minutes or more, and subsequently at a
temperature of about 30.degree. to 100.degree. C., preferably at a
temperature of about 50 to 70.degree. C., for about 16 to 50 hours
or more. Longer residence times may be tolerated without
deleterious results, but tend to yield no commensurate
advantage.
During this subsequent wash step the filament is rendered
substantially free of the spinning solution and coagulation bath.
It has been found that the subsequent hot water wash may be
tolerated by the filament when preceded by the initial cool wash
step. Exhaustive water washing has been found essential in order to
permit effective drawing and to prevent destructive volatilization
of residual solvent and coagulant. The residual solvent content of
the washed filament should contain no more than about 0.1 percent
solvent by weight and preferably no more than about 0.05 percent
solvent by weight.
The initial cold water wash is conveniently conducted in an in line
operation with the filament after it leaves the coagulation bath
continuously passing through a wash medium which is continuously
regenerated. Conventional filament wash rolls may be utilized. The
filament additionally may be washed while wound upon a perforated
bobbin or by the use of any other convenient means as will be
apparent to those skilled in the art.
DRYING OF WASHED FILAMENT
The washed filament is translucent and is next dried by any
convenient means to form a filament which is essentially free of
moisture. For instance, the filament may be continuously passed
over at least one steam heated roll, or the filament while present
on a bobbin may be placed in an oven. Drying may be conveniently
conducted in stages carried out at successively elevated
temperatures. For instance, drying may be conducted for about 24
hours at room temperature, 16 to 24 hours at 110.degree. to
130.degree. C., and for 16 to 100 hours at 160.degree. C. Gradual
drying of the washed filament tends to minimize coalescence. In
order to avoid difficulties created by moisture regain from the
atmosphere during the subsequent drawing step, the dried filament
may be placed under an infrared lamp prior to drawing. For
instance, an infrared lamp may be simply projected onto the feed
bobbin for the drawing zone.
DRAWING OF DRY FILAMENT
The essentially dry filament is next heated at a temperature of
about 450.degree. to 600.degree. C. while simultaneously stretched
about 1.5 to 10 times its original length. The dense uniform
filament microstructure makes possible such relatively high draw
ratios. In a preferred embodiment of the invention the filament is
drawn about 2.5 to 3.5 times its original length while heated at a
temperature of about 475.degree. to 500.degree. C. Temperature
profiling within the draw chamber is recommended in which the
filament is gradually elevated to the draw temperature indicated
over a period of at least one second or more.
The drawing of the filament may be conducted in any convenient
manner such as by applying tension while passing the filament one
or more times over a hot shoe or heated roll, or through a muffle
furnace. The drawing step of the process improves tensile
properties of the filament. Preferred drawing techniques are
disclosed in U.S. Ser. No. 769,862, filed Oct. 23, 1968 in the
names of George F. Ecker and Thomas C. Bohrer, and U.S. Pat. No.
3,541,199 in the names of Thomas C. Bohrer and Arnold J. Rosenthal.
These are assigned to the same assignee as the present invention
and are herein incorporated by reference.
RELAXATION OF DRAWN FILAMENT
The resulting drawn filament optionally next may be relaxed. For
such treatment the drawn filament is heated to a temperature of
about 350.degree. to 525.degree. C., and is allowed to achieve a
relaxation of about 10 to 65 percent in length, and preferably
about 30 to 50 percent in length. A preferred relaxation
temperature is about 425.degree. to 475 C. The relaxation step of
the process renders the filament more highly extensible and greatly
improves the knot strength of the same.
The relaxation step may be conveniently conducted while passing the
drawn filament through a muffle furnace one or more passes or by
passing the same over a hot shoe, or shoes. Other relaxation
techniques will be apparent to those skilled in the art.
High denier polybenzimidazole monofilaments formed in accordance
with the present invention having a denier of a least 100, and
preferably at least 200, and a uniform round cross section find
utility in the manufacture of fibrous closures. For instance, one
member of the closure may contain pile or loops and the other
member inter engageable stiff, resilient hooks generally made by
cutting looped filaments. Separation requires a force of a
considerable magnitude when release of a large number of hooks at
once is attempted, but separation may be quite readily effected by
progressively peeling the layers apart. In specialized uses, these
fibrous closures are preferable to conventional closures, such as
metal zippers since they (1) can be quickly opened, (2) can be
quickly closed, i.e. no special orientation is required, and (3)
cannot get "stuck" or easily break. Air and sea craft represent an
important area where such advantages are highly desirable. Fibrous
closures have heretofore been used in such environments as a means
of quick, easy and reliable attachment and detachment. For example,
fibrous closures are widely used in the interior of commercial
aircraft to permit easy and nondestructive stripping for periodic
examination of the aircraft frame and structure. The
polybenzimidazole filaments of the present process are invaluable
in the production of fibrous closures for use in space and undersea
vehicles where materials which are resistant to flames and high
temperatures are required.
A fibrous closure containing the high denier polybenzimidazole
monofilaments formed in accordance with the present process can be
fabricated in a known manner, as for example that disclosed by De
Mestral in U.S. Pat. Nos. 2,717,437; 3,009,235; 3,154,837 and
3,136,026. For example, they can be woven into the supporting
material in the conventional manner of making a pile fabric and
then cut. In still another method hooking members can be applied to
a plastic support by electrostatic dispersion and gluing. In a
preferred embodiment one member has all the hooks and they are
randomly arranged while the other member has all the loops and they
are oriented. It is of course possible for each member to have
hooks and loops. A small loop can be tied in the monofilament and
contacted with a hot metal surface, e.g. a hot shoe at about
350.degree. to 550.degree. C. for several seconds. Upon cooling and
being untied, the loops will have a permanently set configuration
in the filament and can be repeatedly straightened under tension
without apparent loss of resiliency. This heat-setting operation is
preferably effected in situ, i.e. while an integral part of the
closure member. It may be effected before adhesion, however.
Aside from their use in the aforedescribed closures, the relatively
heavy denier monofilaments can also advantageously replace other
fibrous materials in such uses as high-speed, heat-generating
machinery, firemen's clothing, and the like. In view of their
stiffness and resiliency they may also be used as cleaning,
scouring and/or brushing means such as in clothes brushes and shoe
brushes.
Polybenzimidazole filaments formed in accordance with the present
process of relatively low denier may likewise be utilized in the
formation of heat resistant, nonburning fabrics.
The polybenzimidazole filaments of either high or low denier also
find utility as highly uniform precursors for the production of
carbon or graphite fibrous material upon further thermal treatment.
Such carbon or graphite fibrous materials are particularly useful
as a reinforcing medium when embedded in resinous matrix to form a
strong lightweight structural component. The polybenzimidazole
filaments may additionally be used as substrates for the deposition
of metals such as boron to form similar reinforcing media.
The following examples are given as specific illustrations of the
invention. It should be understood, however, that the invention is
not limited to the specific details set forth in the examples.
EXAMPLE I
A spinning solution having a Brookfield low shear viscosity of 2100
poise at 30.degree. C. is prepared employing dimethylacetamide as
solvent containing 22.5 percent by weight poly[2, 2'
-(m-phenylene)-5, 5' -bibenzimidazole] based upon the total weight
of the solution, and 2 per cent by weight lithium chloride based
upon the total weight of the solution. A preparation of the
polybenzimidazole is described in example II of U.S. Reissue Pat.
No. 26,065.
The spinning solution while at a temperature of 25.degree. C. is
fed to a spinneret having a single hole of 316 micron diameter and
is extruded at a rate of 10 meters per minute into a circulating
coagulation bath of ethylene glycol moving concurrently with the
resulting filament having a temperature of 30.degree. C. The
resulting as-spun filament remains in the coagulation bath for
approximately 5 seconds.
The coagulated filament is passed to an in line wash roll and
washed with circulating water at a temperature of 10.degree. C. for
120 seconds, and then passed to an in line wash roll and washed
with circulating water at a temperature of 30.degree. C. for 170
seconds. Next the filament is pressure washed while present on a
perforated bobbin with circulating water at about 15.degree. C. for
100 hours. The resulting translucent filament is free of residual
quantities of the ethylene glycol coagulation bath and contains
less than 0.05 percent by weight dimethylacetamide.
The filament while present on the perforated bobbin is dried for 20
hours at room temperature (i.e. 25.degree. C.), 16 hours at
115.degree. C., and 100 hours at 160.degree. C. The moisture
content of the dried filament is less than about 0.05 percent by
weight.
The dried filament is drawn at a draw ratio of 3.1:1 while passing
through a Lindberg muffle furnace provided at a maximum temperature
of 510.degree. C. at a supply speed of 20 meters per minute. The
drawn filament is next relaxed (rolls at a ratio of 20:11) 45
percent of its length by passage for a residence time of 16 seconds
through a muffle furnace at 475.degree. C. at a supply speed of 20
meters per minute.
The physical properties (straight tensiles) of the drawn and
relaxed filament are:
Denier per filament 204 Elongation (%) 46.2 Tenacity (grams per
denier) 3.58 Modulus (grams per denier) 69.7
The physical testing is conducted at 70.degree. F. and at 65
percent relative humidity. When submitted to microscopic
examination, the filament exhibits a smooth uniform round cross
section which is free of voids and radial incursions.
EXAMPLE II
A spinning solution having a Brookfield low shear viscosity of 1600
poise at 30.degree. C. is prepared employing dimethylacetamide as
solvent containing 22.0 percent the polybenzimidazole employed in
example I based upon the total weight of the solution, and 2
percent by weight lithium chloride based upon the total weight of
the solution.
The spinning solution while at a temperature of 25.degree. C. is
fed to a spinneret having a single hole of 250 micron diameter and
is extruded at a rate of 20 meters per minute into a coagulation
bath of ethylene glycol having a temperature of 50.degree. C. The
resulting as-spun filament remains in the coagulation bath for 2.5
seconds.
The coagulated filament is passed to an in line wash roll and
washed with circulating water at a temperature of 10.degree. C. for
60 seconds, and then passed to an in line wash roll and washed with
circulating water at a temperature of 80.degree. C. for 85 seconds.
Next the filament is pressure washed while present on a perforated
bobbin with circulating water at about 60.degree. C. for 96 hours.
The resulting translucent filament is free of residual quantities
of the ethylene glycol coagulation bath and contains less than 0.05
percent by weight of dimethylacetamide.
The filament while present on a perforated bobbin is dried for 24
hours at room temperature (i.e. 25.degree. C.), 30 hours at about
105.degree. C., and 96 hours at 160.degree. C. The moisture content
of the dried filament is less than about 0.05 percent by
weight.
The dried filament is drawn at a draw ratio of 3.1:1 in a Lindberg
muffle furnace provided at a maximum temperature of 485.degree. C.
at a supply speed of 10 meters per minute. The drawn filament is
next relaxed (rolls at ratio of 20:10 ) 50 percent of its length by
passage for a residence time of 16 seconds through a muffle furnace
at about 480.degree. C. at a supply speed of 20 meters per
minute.
The physical properties of the drawn and relaxed filament having a
denier per filament of 220 are as follows:
Sraight Tensiles Knot Tensiles
__________________________________________________________________________
Elongation (%) 52 25 Tenacity (grams per denier) 3.15 2.28 Modulus
(grams per denier) 68 --
__________________________________________________________________________
The physical testing is conducted at 70.degree. F. and at 65
percent relative humidity. When submitted to microscopic
examination, the filament exhibits a smooth uniform round cross
section which is free of voids and radial incursions.
EXAMPLE III
Example II is repeated with the exception that the coagulation bath
is glycerol. Smooth uniform filaments are formed having a flat
dogbone configuration which are free of voids and radial
incursions.
EXAMPLE IV
Example II is repeated with the exception that the coagulation bath
is glycerol in admixture with 40 percent water based upon the total
weight of the mixture. Smooth uniform filaments are formed having a
round to oval configuration which are free of voids and radial
incursions.
EXAMPLE V
Example II is repeated with the exception that the coagulation bath
is ethylene glycol in admixture with 20 percent dimethylacetamide
based upon the total weight of the mixture. Smooth uniform round
filaments are formed which are free of voids and radial
incursions.
EXAMPLE VI
Example II is repeated with the exception that the spinneret is
provided with 100 holes of 50 microns each. A continuous
multifilament yarn is formed composed of uniform round filaments
which are free of voids and radial incursions.
Although the invention has been described with preferred
embodiments, it is to be understood that variations and
modifications may be resorted to as will be apparent to those
skilled in the art. Such variations and modifications are to be
considered within the purview and scope of the claims appended
hereto.
* * * * *