U.S. patent number 3,649,196 [Application Number 04/784,947] was granted by the patent office on 1972-03-14 for preparation of carbon paper.
This patent grant is currently assigned to Allied Chemical Corporation. Invention is credited to Edward Reinauer Degginger.
United States Patent |
3,649,196 |
Degginger |
March 14, 1972 |
PREPARATION OF CARBON PAPER
Abstract
A process for preparing fibrous carbonaceous cloth mats or paper
comprising the steps of impregnating a fibrous cellulosic substrate
with an aqueous solution containing borate and polyvinyl alcohol,
allowing the aqueous component of said solution to evaporate from
said impregnated cellulosic substrate, and then carbonizing said
substrate.
Inventors: |
Degginger; Edward Reinauer
(Convent Station, NJ) |
Assignee: |
Allied Chemical Corporation
(New York, NY)
|
Family
ID: |
25134020 |
Appl.
No.: |
04/784,947 |
Filed: |
December 18, 1968 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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768494 |
Oct 17, 1968 |
3542582 |
|
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Current U.S.
Class: |
423/447.5;
423/447.9; 502/427; 427/228 |
Current CPC
Class: |
H01M
4/96 (20130101); D01F 9/16 (20130101); Y02E
60/50 (20130101) |
Current International
Class: |
D01F
9/16 (20060101); D01F 9/14 (20060101); H01M
4/96 (20060101); C01b 031/02 (); C01b 031/07 () |
Field of
Search: |
;23/209.1,209.4,209.5
;8/115.5,115.6,116,119 ;264/29 ;117/46 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Meros; Edward J.
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of my copending
application Ser. No. 768,494 filed Oct. 17, 1968 and issued as U.S.
Pat. No. 3,542,582.
Claims
I claim:
1. A process for the preparation of carbon paper comprising the
steps of:
a. impregnating cellulosic paper having a thickness of up to 30 ml.
with an aqueous solution containing from about 0.5 to about 5.0
weight percent alkali metal borate and from about 0.5 to about 5.0
weight percent water-soluble vinyl alcohol polymer;
b. removing the aqueous component of said solution from said
impregnated paper;
c. carbonizing said impregnated paper by igniting or by roasting at
a temperature of at least about 200.degree. C.
2. A process in accordance with claim 1, wherein said alkali metal
borate is borax.
3. A process in accordance with claim 1, wherein said vinyl alcohol
polymer is substantially fully saponified.
4. A process in accordance with claim 1, wherein said borate and
said vinyl alcohol polymer are each present in said aqueous
solution at a concentration ranging from about 1.0 to about 3.0
weight percent.
5. A process in accordance with claim 1, wherein said carbonizing
is effectuated by roasting at a temperature of at least about
200.degree. C.
Description
BACKGROUND OF THE INVENTION
The invention relates to a process for the transformation of an
intertwined, fibrous cellulosic material into a carbon fiber having
substantially the same structural form as the cellulosic
precursor.
More particularly, the invention relates to a process for the
preparation of carbon cloth, paper, or matting useful as a catalyst
support or filtration medium or in other applications which can
advantageously utilize carbon in these structural forms.
Still more particularly, this invention relates to the preparation
of interlaced or intertwined fibrous carbon mats, papers, cloths,
or the like, from a mat, paper, or cloth, or other fibrous form of
cellulose using an aqueous solution containing borate and polyvinyl
alcohol.
Carbon is well known to be substantially inert to most organic and
inorganic chemical reagents such as organic solvents, inorganic and
organic acids, aqueous caustic, and the like. Because of this
chemical inertness, carbon is widely used as a catalyst support or
as a filtration medium. In the latter field of application, the
fact that carbon will preferentially adsorb certain polar organic
compounds makes it particularly useful. Unfortunately, the fact
that carbon is currently readily available only in the form of
solid chunks or powder, e.g., charcoal briquettes or carbon black,
limits its utility in some instances. In many cases, it is
desirable to have carbon in fibrous form, e.g., a mat, paper, or
cloth that is an integral and self-supporting, but nonetheless
porous or foraminous, unit.
Although carbon filaments are known, to date, I have been unable to
discover any teaching of a practical, inexpensive way to make an
intertwined fibrous carbon, e.g., a carbon cloth, paper, or
mat.
SUMMARY OF THE INVENTION
It is an object of this invention to provide an efficient and
inexpensive process for the production of carbon cloths, mats,
papers, and the like.
Further objects and advantages will become apparent from the
description of the invention which follows in greater detail.
The invention comprises impregnating a fibrous cellulosic material,
hereinafter referred to as "substrate," with borate-polyvinyl
alcohol aqueous solution, as hereinafter more specifically defined,
removing the water component of such solution from the impregnated
cellulosic substrate, preferably by evaporation, and then igniting
or roasting the thus-treated cellulosic substrate which is thereby
transformed into its carbon counterpart.
The cellulosic substrates which are amenable to transformation into
their structurally analogous carbon counterpart include any
fibrous, intertwined cellulosic material such as cotton batting,
woven or knitted cotton or linen cloth, felted cotton or linen,
paper such as kraft paper, cardboard, chipboard, cellulose-based
roofing felt, cotton or linen twine or rope, and hemp, jute, fiber,
kapot, and similar processed, unprocessed, or partially processed,
fibrous cellulosic matter.
The term "paper" as used herein connotes felted or matted sheets of
cellulosic fibers, which sheets can be up to about 30 mil
thick.
The carbon paper produced by the process of the instant invention
is, of course, not in any way related to the coated reproducing
paper ordinarily referred to as "carbon paper." The carbon paper of
the instant invention contemplates felted or matted sheets of
carbon fibers structurally analogous to its cellulosic
precursor.
When such a fibrous cellulosic substrate is exposed, without
treatment in accordance with the instant invention, to flame or to
a temperature above its ignition point, it will decompose giving
off flammable gases which, if sufficient air is present, also
ignite and tend to further increase the temperature of the
cellulosic substrate, thereby increasing its rate of decomposition.
If the cellulosic substrate is exposed to a flame in the presence
of excess air, it will ignite and burn. This burning continues
until only carbonaceous material remains, whereupon the flame
generally subsides, but the oxidation of the carbonaceous residue,
i.e., afterglow, continues, until the initially formed carbonaceous
residue is substantially totally consumed. For example, cotton
cloth or paper will burn and then glow until only a small amount of
fragile, crumbly ash remains. If the cellulosic substrate is heated
above its combustion temperature in the absence of an open flame,
it will either ignite and carbonize or carbonize without ignition
depending upon whether an excess, or merely a stoichiometric,
quantity of air is present. In either event, crumbly ash will be
formed.
However, if the fibrous cellulosic substrate, e.g., cheesecloth or
paper, which has been impregnated in accordance with the teaching
of my invention, is exposed to a flame, it will ignite and burn,
but, it will burn only to the point of forming a structurally
analogous carbon counterpart, i.e., a carbon cheesecloth or carbon
paper. It will not burn to a crumbly ash having little or no
structural integrity. Likewise, if the cellulosic substrate,
impregnated in accordance with the teaching of the instant
invention, is heated, i.e., roasted, above about 200.degree. C. in
the absence of an open flame, it will again form a structurally
analogous carbon counterpart and will not go to a crumbly ash.
Thus, the cellulosic substrate treated according to my invention
carbonizes to its structural analog and is not completely destroyed
by ignition or roasting.
The impregnation of the fibrous cellulosic substrate with the
borate-polyvinyl alcohol mixture in accordance with my invention
may be carried out by any of the known conventional procedures
utilized for the impregnation of cellulosic fiber with materials
which are water soluble. For example, the cellulosic substrate may
be immersed in the borate-polyvinyl alcohol aqueous solution, or
the solution may be brushed or sprayed on the fibrous cellulosic
substrate. After impregnation, the aqueous component of the
solution is allowed to evaporate from the impregnated cellulosic
fiber substrate leaving the borate and polyvinyl alcohol
constituents of the solution both within and on the surface of the
substrate. Such evaporation of the water may be effectuated either
at ambient or above ambient temperature.
It is desirable that the amount of the combined borate and
polyvinyl alcohol constituents of the aqueous impregnating solution
which remains within or on the surface of the cellulosic substrate
after evaporation of the water shall be from about 5 to about 40
percent by weight of the weight of the cellulosic substrate,
preferably from about 10 to about 30 weight percent.
The solutions used in the practice of the instant invention are
aqueous solutions containing (a) from about 0.5 to about 5.0
percent by weight of an alkali metal borate; and (b) from about 0.5
to about 5.0 percent by weight of a water-soluble polymer of vinyl
alcohol. Such solutions are disclosed and claimed in copending
commonly assigned U.S. application Ser. No. 602,760 filed Dec. 19,
1966.
The term "alkali metal borate" embraces not only the alkali metal
salts of the common boric acids, i.e., tetraboric acid, H.sub.2
B.sub.4 O.sub.7, meta-boric acid, HBO.sub.2, and ortho-boric acid,
H.sub.3 BO.sub.3, but also the alkali metal salts of the other
boric acids such as H.sub.2 B.sub.2 O.sub.4, H.sub.2 B.sub.6
O.sub.10, H.sub.2 B.sub.8 O.sub.13, H.sub.2 B.sub.12 O.sub.19,
H.sub.6 B.sub.4 O.sub.9, and H.sub.6 B.sub.8 O.sub.15. With the
exception of meta- and ortho-boric salts, such alkali borates have
the general formula: M.sub.2 O.sup.. mB.sub.2 O.sub.3, wherein M
denotes an alkali metal and m can range from 1 to 4. Hydrates of
any of the foregoing borate salts are also suitable. The preferred
borate is borax, i.e., sodium tetraborate decahydrate.
The term " water-soluble vinyl alcohol polymer" embraces vinyl
alcohol polymers having up to 50 percent of the hydroxyl groups
thereof replaced by methoxy, ethoxy, acetyl, propionyl or butyryl
radicals; i.e., partially etherified or esterified polyvinyl
alcohol. Said methoxy and ether radicals can be unsubstituted or
substituted with hydroxyl or carboxyl groups. Said acetyl,
propionyl and butyryl radicals can likewise be unsubstituted or can
be halogen- or hydroxyl-substituted. Preferably, no more than about
20 percent of the polyvinyl alcohol hydroxyl groups will be
replaced by any of the aforementioned ether or ester radicals.
The vinyl alcohol polymers utilized in the practice of the instant
invention can, therefore, be represented by the structure:
wherein x can range from about 1,200 to about 5,000, preferably
1,600 to 3,000, and wherein R represents hydrogen-, methyl-,
ethyl-, acetyl-, propionyl-, butyryl-, hydroxyl-, or
carboxyl-substituted methyl or ethyl, or halogen- or
hydroxyl-substituted acetyl, -propionyl or butyryl, and wherein at
least about 50 percent of said R groups are hydrogen. As heretofore
indicated, preferably at least about 80 percent of said R groups
will be hydrogen.
The water-soluble vinyl alcohol polymers of the instant invention
have molecular weights ranging from about 50,000 to about 450,000,
preferably 70,000 to 200,000.
Polyvinyl alcohol is conventionally obtained by polymerizing esters
of vinyl alcohol followed by removal of the ester groups by
saponification. To prepare the vinyl alcohol polymers of the
instant invention, wherein up to about 50 percent of the hydroxyl
groups are ester substituted, it is merely necessary to polymerize
the corresponding vinyl ester and then partially saponify the
resulting polyvinyl ester and thereby remove 50 percent or more of
the ester groups. For example, to prepare polyvinyl alcohol
containing 20 percent acetyl groups, a polyvinyl acetate polymer
would be 80 percent saponified and the remaining 20 percent acetyl
groups left unsaponified. A 99+ percent polyvinyl alcohol is
substantially fully saponified. To prepare the methoxy- and
ethoxy-ether derivatives of polyvinyl alcohol, a polyvinyl alcohol
having substantially 100 percent hydroxyl groups is etherified up
to the desired degree, i.e., up to about a maximum of 50 percent
using conventional etherification agents such as diazomethane,
dimethyl sulfate, or diethyl sulfate.
The preferred concentration of alkali metal borates and of vinyl
alcohol polymers in the solution of the instant invention ranges
from about 1.0 to about 3.5 percent by weight of each.
The aqueous borate-vinyl alcohol polymer of the instant invention
can be prepared by adding the appropriate quantity of borate and
vinyl alcohol polymer either simultaneously or consecutively to the
water, preferably with agitation, to ensure rapid dissolution of
the borate and vinyl alcohol polymer. Most preferably such water is
heated up to about 95.degree. C. to further enhance the rate of
dissolution. Alternatively, aqueous solutions of borate and of
vinyl alcohol polymer can be prepared separately and then
combined.
The following specific examples further illustrate my
invention.
EXAMPLE 1
Ten grams of 87-89 percent hydrolyzed polyvinyl alcohol (PVA)
(Vinol 523, Airco Chemicals and Plastics) is added to 750 grams of
water heated at 70.degree. - 90.degree. C. The PVA dissolves
virtually instantaneously. A second solution is prepared by
dissolving 10 grams of borax in 230 grams of water at 85.degree. C.
The two solutions are then combined. A 1-square-foot piece of
ordinary cheesecloth is immersed in 100 cc. of the combined
solution for a few seconds, removed, excess fluid squeezed out, and
the cloth air-dried. Weighing after drying indicates a 25 percent
weight gain. The dried, impregnated cheesecloth is ignited over its
entire surface with a bunsen burner. It burns to the carbon cloth
counterpart of the cheesecloth.
EXAMPLE 2
A 1-foot-square swatch of shirting grade, 100 percent cotton
broadcloth is immersed for about 30 seconds in 150 cc. of aqueous
solution containing 1.5 weight percent borax and 1.5 percent (99+
percent hydrolyzed) PVA. The swatch is removed, squeezed to remove
excess liquid, air-dried, and roasted in a closed oven at
350.degree. C. for 30 minutes. The resultant product is a
fine-weave carbon fabric.
EXAMPLE 3
Strips of shirting grade 100 percent cotton broadcloth 3.times. 6
inches are immersed for 1 minute in one of the solutions tabulated
below, removed, and air-dried for 24 hours at room temperature. The
impregnated strips are then mounted horizontally and ignited with a
match at one corner. Samples 1-3 burn up completely leaving only a
small amount of crumbly unstructured ash. Samples 4-13 burn to a
carbon cloth having the same woven structure as the original cotton
cloth.
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COMPOSITIONS OF AQUEOUS TREATING SOLUTIONS
polyvinyl Alcohol.sup.1 Borate.sup.2 Sample No. Compound Weight %
Compound Weight %
__________________________________________________________________________
1 (untreated) -- -- -- -- 2 -- -- A 3.0 3 A 3.0 -- -- 4 A 1.0 B 1.0
5 B 1.0 A 1.0 6 A 3.0 B 3.0 7 B 3.0 B 3.0 8 C 3.0 B 3.0 9 D 3.0 B
3.0 10 A 3.0 A 3.0 11 B 3.0 A 3.0 12 C 3.0 A 3.0 13 D 3.0 A 3.0
__________________________________________________________________________
.sup.1 Polyvinyl Alcohol A: 99+% polyvinyl alcohol, i.e., at least
99% saponified polyvinyl acetate. M.W.=70,000 B: 80% polyvinyl
alcohol. M.W.=200,000 C: 50% polyvinyl alcohol. M.W.=100,000 D:
polyvinyl alcohol 30% ethoxylated. M.W.=75,000 .sup.2 Borate A:
borax, i.e., sodium tetraborate decahydrate B: potassium
tetraborate pentahydrate
EXAMPLE 4
In a 2,000 -cc. beaker is placed 1,600 cc. of aqueous solution
containing 3.0 weight percent borax and 3.0 weight percent 99+
percent hydrolyzed PVA. A variety of fibrous cellulosic substrates
are consecutively immersed in this solution, removed, pressed to
remove excess liquid, air-dried, and roasted for one-half hour at
300.degree. C. in a closed oven. In all cases, the treated material
forms its carbon structural analog and does not degrade to a
fragile ash. The thus-treated substrates are listed below, along
with the weight gain by impregnation.
Substrate Weight Gain (%)
__________________________________________________________________________
Cotton-wool 39 Linen suiting 31 Cotton rope, 1/4" dia. 26 Jute
fiber 17 Kapok 10
__________________________________________________________________________
EXAMPLE 5
Part A. Preparation of Palladium-Carbon Hydrogenation Catalyst
One hundred and eighty grams of 1/4-inch-diameter cotton rope cut
in 3-inch lengths is immersed for 30 seconds in a 1-liter solution
containing 3 weight percent borax and 3 weight percent 99+ percent
hydrolyzed PVA. The samples of rope are then drained, dried in the
atmosphere, placed on a glass tray, and roasted in a closed oven at
400.degree. C. for 1 hour. On removal from the oven, the carbon
structural analog of the rope is obtained. The carbon rope is
heated on a steam bath with 10 percent nitric acid for 3 hours,
washed free of acid with distilled water, and dried at 100.degree.
C.
Nine grams of this acid-washed carbon rope is added to a mixture of
10 ml. of an aqueous palladium chloride solution containing 0.1
gram of palladium and approximately 0.05 gram of hydrogen chloride
per milliliter and a solution of 27 grams of sodium acetate
trihydrate in 100 ml. of water. The carbon rope-containing mixture
is then placed in a Parr bomb and hydrogenated at 50 p.s.i. H.sub.2
pressure until hydrogen absorption ceases. The carbon rope is then
separated from the solution, washed with water, and dried with an
airstream for 30 minutes.
Part B. Reduction of Dihydro-.alpha.-Naphthol Using the
Palladium-on-Carbon-Rope Catalyst Prepared in Part A
One hundred and six grams of industrial grade
5,8-dihydro-1-naphthol, (m.p. 69.degree. - 72.degree. C.) dissolved
in 250 ml. of ethyl acetate, is placed in a 1-liter Parr bomb. Five
grams of the palladium-on-carbon-rope catalyst (prepared in part A)
is added to the bomb, the bomb then sealed and shaken for 45
minutes with 3 atm. hydrogen pressure maintained in the bomb during
the shaking period. The palladium-on-carbon-rope catalyst is
removed by filtration, the filtrate evaporated, leaving 105 grams
of an oil which quickly solidifies on standing (m.p. 67.degree. -
69.5.degree. C.).
Recrystallization from 250 ml. petroleum ether (b.p. 98.degree. C.)
affords 93 grams of colorless crystals of
tetrahydro-.alpha.-naphthol (m.p. 68.degree. - 68.5.degree.
C.).
EXAMPLE 6
Use of Carbon Cloth as a Filtration Medium
One hundred cubic centimeters of a methanol solution of impure
ethylene glycol is filtered through a mat of 100 grams of the
carbon cloth prepared as in Example 3, and placed in a Buchner
funnel. Prior to filtration, the methanol solution is an amber
color. Following filtration through the carbon cloth mat, the
solution is a straw color.
EXAMPLE 7
A 1-foot square piece of unbleached kraft paper 10 mils thick was
fully immersed for 2 minutes in 100 cc. of an aqueous solution
containing 1.5 weight percent each of borax and of 99+ percent
hydrolyzed polyvinyl alcohol. The paper was removed, excess liquid
removed, the paper then air-dried, and ignited at one lower corner
while being held vertically. It burned to the carbon analog of the
kraft paper.
Using the same method, 40-mil thick chipboard, 10-mil thick
bleached kraft paper, and a 15 -lb. (15 lb./100 sq. ft.)
cellulose-based roofing felt were transformed into their carbon
counterparts.
Various modifications will be apparent to one skilled in the art,
and it is not intended that his invention be limited to the details
in the specific examples presented by way of illustration.
Accordingly, the scope of the invention is limited only by the
appended claims.
* * * * *