U.S. patent number 3,720,759 [Application Number 05/039,517] was granted by the patent office on 1973-03-13 for process for the production of carbon and graphite fibers.
This patent grant is currently assigned to Sigri Elektrographit GmbH. Invention is credited to Dietrich Overhoff.
United States Patent |
3,720,759 |
Overhoff |
March 13, 1973 |
PROCESS FOR THE PRODUCTION OF CARBON AND GRAPHITE FIBERS
Abstract
Carbon fibers are produced by treating synthetic polymeric
fibers with a solution of a condensation agent at a temperature of
180.degree. to 230.degree.C to effect cross-linking and/or
cyclization within the polymeric fibers and thereafter heating the
treated fibers to a temperature between 200.degree.-300.degree.C in
an atmosphere containing an oxidizing gas and, subsequently, in an
inert or reducing atmosphere, to a temperature of at least about
1,000.degree.C. Titanium tetrachloride, lead tetrachloride, tin
tetrachloride, and tin tetrabromide are used as condensation
agents, preferably in the form of complexes in a solvent such as
high-boiling ethers and esters. Dimethylformamide is used as a
complex former. o-nitroanisole, d-n-butylterephthalate, and
iso-octadecylbenzoate are used as both solvent and complex
former.
Inventors: |
Overhoff; Dietrich (Augsburg,
DT) |
Assignee: |
Sigri Elektrographit GmbH
(Augsburg, DT)
|
Family
ID: |
5767285 |
Appl.
No.: |
05/039,517 |
Filed: |
May 21, 1970 |
Foreign Application Priority Data
|
|
|
|
|
Apr 7, 1970 [DT] |
|
|
P 20 16 445.8 |
|
Current U.S.
Class: |
423/447.5;
8/115.56; 8/115.68; 423/447.6; 8/115.65; 264/DIG.19; 423/447.7 |
Current CPC
Class: |
D01F
9/22 (20130101); Y10S 264/19 (20130101) |
Current International
Class: |
D01F
9/14 (20060101); D01F 9/22 (20060101); C01b
031/07 () |
Field of
Search: |
;30/209.1,209.2,209.4
;8/115.5 ;117/46 ;423/447 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Meros; Edward J.
Claims
I claim:
1. Method of producing a carbonaceous fiber from a thermoplastic
polymeric fiber selected from polyacrylonitrile and
polyacrylonitrile copolymers, comprising the steps of:
a. stretching or elongating the polymeric fiber to a stretching
ratio of at least 1:4 until the tensile strength of the stretched
fiber is at least 4 p/den;
b. heating the fiber in a solution of a solvent selected from
o-nitroanisole, di-n-butylterephthalate or i-octadecylbenzoate
containing a complex of said solvent and a halide selected from the
group consisting of titanium tetrachloride, lead tetrachloride, tin
tetrachloride and tin tetrabromide, to a temperature of 180 to
230.degree.C; and
c. heating the fiber without external tensile stress to a
temperature between 200.degree. and 300.degree.C in an atmosphere
containing oxidizing gases and, subsequently, in an inert or
reducing atmosphere, to approximately 1,000.degree.C.
2. The method of claim 1, wherein di-n-butylterephthalate is used
as both complexing agent and solvent for lead tetrachloride.
3. The method of claim 1, wherein iso-octadecylbenzoate is used as
both complexing agent and solvent for tin tetrabromide.
4. The method of claim 1, wherein the solution contains at least
0.8 percent by weight of a complex of said halide.
5. The method of claim 4, wherein the solution contains from 1.0 to
1.5 percent by weight of a complex of said halide.
6. The method of claim 1, wherein the synthetic polymeric fiber is
a copolymer of acrylonitrile and methylmethacrylate.
7. The method of claim 1, wherein the fiber in step (c) is heated
to 2,500.degree.C.
Description
My invention relates to a method of improving the suitability of
synthetic polymer fibers for carbonization.
The production of carbon and graphite fibers by carbonization
followed, if desired, by graphitization of synthetic polymer fibers
such as regenerated cellulose, polyacrylonitrile or
polyvinylchloride is already known. The synthetic polymer fibers
are heated in an inert and/or reducing atmosphere to a temperature
up to about 1,000.degree.C, for the purpose of graphitization, the
carbon fibers so produced are then further heated in an inert
atmosphere up to a temperature in the region of 2,500.degree.C. It
has been found that the synthetic polymer fibers are partially
depolymerized during their conversion to carbon fibers,
particularly at temperatures within the range of from 200.degree.
to 500.degree.C which the carbon content and, more important, the
strength of the fibers decrease.
A number of methods of overcoming these problems have been
described. For example, U.S. Pat. No. 2,697,028, describes methods
of increasing the carbon yield, and thus also the strength of the
fibers, by heating the synthetic polymer fibers in air at
temperatures between 200.degree. and 300.degree.C, or by the
addition of depolymerization inhibitors, such as ammonia, sulfur
dioxide or methylamine. However, the improved strength produced is
insufficient for many uses of the carbon fibers. High strength
values are particularly required for those carbon and graphite
fibers, which are to be used for the reinforcement of synthetic
plastics, metals and ceramic materials.
It has also been proposed to improve the strength and rigidity of
carbonized fibers by stretching the fibers at high temperatures in
a direction parallel to the fibers axis. For example, in British
Pat. No. 1,148,872, a method is described in which
polyacrylonitrile is heated in a non-oxidizing atmosphere to at
least 1,000.degree.C while simultaneously being held under tension
so that the final length of the fibers is greater than the initial
length thereof. U.S. Pat. No. 3,454,362 describes a method in which
carbon or graphite fibers are subjected to a longitudinal tensile
stress at temperatures above the flow temperature of the carbon
fibers so that the fibers are stretched by at least 1 percent. Very
high temperatures will be required for such a method.
The stretching of partially or completely carbonized fibers at
temperatures greater than 200.degree.C causes a substantial
alignment of the molecules in the direction of the fiber axis and
results in a considerable increase in the strength and elasticity
modulus values of the fibers. However, a disadvantage of such
procedures is that complicated apparatus is necessary for
stretching the fibers at relatively high temperatures and any
breakages which occur in the fibers result in relatively long
stoppages in production.
It is an object of my present invention to overcome or at least
mitigate the aforesaid disadvantages and to provide carbon and
graphite fibers having high strength values.
According to the present invention there is provided a method
improving the suitability for carbonization of a non-cellulosic
synthetic polymer fiber, in which the fiber is contacted with one
or more condensation agents in order to effect cross-linking
between and/or cyclization within polymer molecules, the synthetic
polymer fiber then being oxidized by heating in the presence of a
dehydrating agent at a temperature or temperatures within the range
of from 175.degree. to 350.degree.C while free of any substantial
tension.
The present invention is applicable to the majority of
non-cellulosic synthetic polymer fibers since most fibers, if not
all fibers, of this type are capable of undergoing intra-molecular
cylization within and/or a certain amount of cross-linking between
polymer chains leading to formation of a kind of "ladder" polymer.
The most suitable polymers for use in the method of the invention
are polymers, and copolymers with suitable copolymerizable
monomers, of acrylonitrile. However, polymers and copolymers of
vinylchloride, vinylesters and vinylalcohol, and
1,2-cis-polybutadiene can also be used. The intramolecular and/or
intra-molecular reactions which take place in the presence of the
condensation agents result in the substantial retention of the
molecular orientation during the subsequent heating of the fibers
in an oxidizing atmosphere and later in an inert or reducing
atmosphere.
The nature of the inter-molecular and/or intra-molecular reactions,
which occur will of course depend upon the particular polymer used.
In the case of polyacrylonitrile, the cyclizing and/or
cross-linking pre-treatment takes place in a similar manner to the
reaction which has been observed with monomeric acrylonitrile which
can undergo cyclization to yield dihydropyridine derivatives. A
reaction similar to cyclization of acrylonitrile occurs with
polyacrylonitrile, leading to a cross-linked product which contains
dihydropyridine rings.
The reaction in the presence of a condensing agent or catalyst is
generally carried out at temperatures of from 180.degree. to
230.degree.C and preferably from 190.degree. to 200.degree.C. The
cross-linking agents used are generally Lewis acids of a strength
sufficient to saturate the free pairs of electrons of the polymer.
While sulfur trioxide, for example, can be used as condensation
catalyst, this is not a convenient material for working with on an
industrial scale. The preferred catalysts for use in the method
according to the present invention are halides of elements of the
fourth main group and sub-group of the Periodic Table. Particularly
preferred condensation agents are titanium tetrachloride, lead
tetrachloride, tin tetrachloride and tin tetrabromide.
It has been found particularly advantageous to use the condensation
agents in the form of complexes, more especially in the form of
amine complex compounds, ester complex compounds or ether complex
compounds. A particular advantage of the use of complexes is that
the above-mentioned halide condensation agents are normally highly
hydroscopic, but in the form of complex compounds, they possess a
substantially grater water resistance. The complexes are used in
solution in suitable solvents such as high-boiling ethers and/or
esters. Those solvents which are at the same time complex formers
are particularly advantageous. Examples of compounds which can be
used as both solvent and complex former are o-nitroanisole,
di-n-butylterephthal-ate and iso-octadecylbenzoate.
Dimethylformamide can be used simply as complex former. When the
synthetic polymer fibers are immersed in a solution of a
condensation agent, the solution advantageously contains at least
0.8 percent by weight, and preferably from 1.0 to 1.5 percent by
weight, of the condensation agent in the form of a complex.
The on-cellulosic synthetic polymer fibers used in the process of
the present invention are advantageously subjected to stretching at
low temperature, generally the ambient temperature, prior to being
contacted with the condensation agent at an elevated temperature.
The stretch ratio to which the fibers are subjected is
advantageously at least 1:4 and the tensile strength of the
stretched fibers should be at least 4 P/den. (pond per denier).
This preliminary step, of course, is commonly used in the textile
art and serves to align the polymer molecules.
Advantages of the use of the method of the present invention are as
follows:
A. Carbon and graphite fibers of high strength can be obtained from
fibers pretreated in the aforespecified manner;
B. the need to subject the fibers to stretching at elevated
temperatures is obviated so that complicated equipment is no longer
required and stoppages in production caused by breakages in the
fibers are avoided; and
C. the pretreatment of synthetic polymer fibers prior to
carbonization and graphitization can be carried out in a very short
time. The fibers can be carbonized and, if desired, graphitized in
the same oven as that used in the oxidation step.
During the oxidation step, the temperature of the fibers is
advantageously gradually raised at a rate of from 40.degree. to
200.degree.C per hour. In a preferred mode of operation, oxidation
is carried out at temperatures within the range of from 200.degree.
to 300.degree.C, the temperature of the fibers being increased at a
rate of 100.degree.C per hour during oxidation. The oxidation step
is advantageously carried out at a temperature of from 180.degree.
to 250.degree.C and can be completed in from 1 to 5 hours. The
dehydrating agent used is advantageously air, although chlorine or
liquid sulfur can be used for this purpose.
The following Examples illustrate the invention:
EXAMPLE 1
Fibers of a copolymer of 95 percent by weight acrylonitrile and 5
percent by weight methyl methacrylate were stretched while wet to
five times their original length. The tensile strength of the
stretched fibers was 4 ponds/den. The fibers were then dried at a
temperature of 120.degree.C and pulled over rollers while free of
any tension other than that required to pull them over the rollers,
through a tank containing a 1.5 percent solution of PbC1.sub.4
.sup.. 2 di-n-butyltere-phthalate in di-n-butylterephthalate. The
bath temperature was 200.degree.C and the residence time of the
fibers there was about 30 minutes. The fibers were then drawn
through the nip of wringer rollers and led into a second tank
containing acetone in which the di-n-butylterephthalate was washed
off them. The fibers were then washed in a third tank containing
water and dried in a tube dryer at about 120.degree.C.
The fibers were then subjected to an oxidation treatment. For this
purpose, they were heated in a tube furnace in which the
temperature control was such that a linear rise in temperature of
100.degree.C per hour was obtained in a temperature range of
200.degree. to 300.degree.C. During the residence of the fibers in
the tube furnace, a stream of air was continuously passed through
the furnace.
The oxidized fibers were then subjected to carbonization. For this
purpose, they were pulled through a second furnace to which a
stream of nitrogen was continuously passed, the temperature control
in the second furnace being such that there was a linear rise in
temperature of about 2,000.degree.C per hour in the temperature
range between 300.degree. to 1,000.degree.C. The fibers were
subsequently further heated in a nitrogen atmosphere to
1,700.degree.C, the temperature control being such that a linear
rise in temperature of 5,000.degree.C per minute occurred.
After the carbonization, the fibers had the following mechanical
properties:
E (Elasticity modulus) = 2.00 .times. 10.sup.6 kp/cm.sup.2
.delta. (Tensile strength) = 2.1 .times. 10.sup.4 kp/cm.sup.2
EXAMPLE 2
A copolymer of about 95 percent by weight acrylonitrile and about 5
percent by weight methylmethacrylate was dry stretched to a stretch
ratio of 1:6. The stretched fibers, which had a tensile strength of
7 ponds/den. were immersed in iso-octadecylbenzoate containing
dissolved therein 1 percent by weight of a complex of SnBr.sub.4
and iso-octadecylbenzoate. The temperature of the solution was
190.degree.C and the fibers were immersed therein for 60 minutes.
The fibers were then washed, oxidized and carbonized in the manner
set out in Example 1. The fibers obtained after carbonization had
the following mechanical properties:
E = 2.55 .times. 10.sup.6 kp/cm.sup.2
.delta. = 2.6 .times. 10.sup.4 kp/cm.sup.2
* * * * *