U.S. patent number 3,654,940 [Application Number 05/092,837] was granted by the patent office on 1972-04-11 for method for removing resinous or rubber deposits with organic peroxides.
This patent grant is currently assigned to Chemed Corporation. Invention is credited to Jack Ritzi.
United States Patent |
3,654,940 |
Ritzi |
April 11, 1972 |
METHOD FOR REMOVING RESINOUS OR RUBBER DEPOSITS WITH ORGANIC
PEROXIDES
Abstract
Method for removing resinous and rubber films and other deposits
from processing equipment or other coated surfaces comprising first
applying to the deposit a catalyzed organic solvent solution of an
organic peroxide, then activating decomposition of the
peroxide-treated deposit by heating for about 15 minutes to about 4
hours at temperatures of about 100.degree. to about 240.degree.
Fahrenheit, and simultaneously or subsequently subjecting the
"scorched" deposit to the action of an alkaline aqueous cleaning
solution.
Inventors: |
Ritzi; Jack (Hamilton, OH) |
Assignee: |
Chemed Corporation (Cincinnati,
OH)
|
Family
ID: |
22235402 |
Appl.
No.: |
05/092,837 |
Filed: |
November 25, 1970 |
Current U.S.
Class: |
134/2; 134/29;
134/38; 510/202; 510/213; 510/371; 510/376; 510/508; 510/204;
510/201; 510/372 |
Current CPC
Class: |
C09D
9/00 (20130101); C23G 5/00 (20130101); C08F
2/008 (20130101) |
Current International
Class: |
C23G
5/00 (20060101); C09D 9/00 (20060101); C08F
2/00 (20060101); B08b 003/08 () |
Field of
Search: |
;134/2,4,29,38,22,39
;252/94,95,96 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Wolk; Morris O.
Assistant Examiner: Marantz; Sidney
Claims
What is claimed is:
1. Method for removing undesirable resinous or rubber deposits from
substrates bearing the same comprising:
a. first applying to the deposit a solution of an organic peroxide
and a peroxide decomposition catalyst in an organic solvent;
b. then activating decomposition of the peroxide treated deposit by
heating at a temperature of from about 100.degree. to about
240.degree. Fahrenheit for a period of from about 15 minutes to
about 4 hours;
c. simultaneously with or subsequent to step (b), subjecting the
deposit to the action of an aqueous alkaline cleaning solution to
remove at least a portion of the undesirable deposit from the
substrate.
2. Method of claim 1 wherein the undesired deposit is Neoprene
rubber.
3. Method of claim 1 wherein the undesired deposit is poly(vinyl
acetate).
4. Method of claim 1 wherein the undesired deposit is cured
automobile tire compound.
5. Method of claim 1 wherein the aqueous alkaline cleaning solution
employed in step (c) comprises at least about 2 percent by weight
of free alkali metal hydroxide.
6. Method of claim 5 wherein the alkali metal hydroxide is sodium
hydroxide.
7. Method of claim 1 wherein the peroxide employed in step (a) is
di(tertiary-butyl) peroxide or tertiary-butyl perbenzoate.
8. Method of claim 7 wherein the peroxide decomposition catalyst is
a heavy metal salt of a fatty acid having from about seven to about
24 carbon atoms.
9. Method of claim 8 wherein the metal salt is cobalt naphthenate.
Description
This invention relates to methods for removing undesirable resinous
and rubber films or other deposits from processing equipment or
other substrates coated therewith. In particular it relates to an
improved two-step method which provides much faster removal of the
undesired deposits.
In Kahn et al., U.S. Pat. No. 3,285,777 the patentees have
disclosed a method for cleaning processing equipment with organic
solvent solutions of up to about 20 percent by weight of an organic
hydroperoxide and small amounts of a metallic compound to serve as
peroxide decomposition catalyst. The method as disclosed requires
continuous immersion of the contaminated surface for treatment
times of 24 hours or more, in some cases up to as many as 6
days.
It is common practice in the paint stripping art to subject items
to be stripped to alkaline stripping solutions, e.g., Kirk-Othmer
Encyclopedia of Chemical Technology, Second Edition, Volume 14
(1967), pp. 490-491 and references cited at pages 492 and 493; and
Goldsmith et al., U.S. Pat. No. 3,410,805. The disclosures of Kirk
Othmer and Goldsmith et al., are hereby incorporated herein by
reference.
It has now been discovered that the cleaning method suggested by
Kahn et al., can be improved and greatly accelerated by a
modification thereof and a sequential or simultaneous combination
with a treatment with aqueous alkaline cleaning solutions,
especially highly alkaline solutions of the type known in the paint
stripping art.
Accordingly, the present invention provides a rapid efficient
method for removing resinous and rubber deposits from substrates
(e.g., processing equipment) to which they are adhered by applying
to the deposit a solution of a mild organic peroxide and a metal
soap catalyst in an organic solvent, thereafter heating the
peroxide-treated deposit at an elevated temperature for a short
time to at least partially decompose ("scorch") the deposit and
then simultaneously or subsequently subjecting the scorched deposit
to an aqueous alkaline cleaning solution to strip the scorched
deposit from the substrate. Total treatment time required to remove
the deposit can be reduced to as little as 30 minutes or so and
seldom if ever exceeds about 1 hour although times up to about 4
hours are sometimes desirable.
The method of this invention is applicable to the removal of
virtually any resinous or rubber film or other deposit. Among those
to which the invention can be applied are the organic deposits
described in the Kahn et al patent, as well as undesired deposits
of olefin polymers and copolymers, vinyl and vinylidene polymers
and copolymers, and various natural and synthetic rubbers; e.g.,
polyethylene, polypropylene, polybutadiene, polyvinylchloride,
polyvinyl acetate, Neoprene, cured natural rubber, cured synthetic
rubbers, and the like.
The organic peroxide solutions used in the initial step of the
method of this invention have the following composition:
Weight Percent Ingredient Operable Preferred Organic solvent 40 to
89 about 65 Peroxide 10 to 50 about 30 Metal catalyst 1 to 10 about
5
The organic solvent may be any organic liquid which is
substantially inert with respect to the peroxide and which
dissolves substantially all of the peroxide and metal catalyst
compound. Operable solvents include aliphatic, alicyclic and
aromatic compounds and mixtures thereof including for example,
hexane, heptane, isooctane, toluene, benzene, kerosene, benzene,
monochlorobenzene and the like.
The peroxides used in the practice of the invention are mild
organic peroxides, i.e., those which have a half life (measured in
dilute benzene solutions) greater than about 1 hour at 212.degree.
Fahrenheit and which thus can (although not recommended for long
periods) be handled and stored at ambient temperatures without
excessive danger. Representative examples of such peroxides are
di-(tertiary-butyl) peroxide, tertiary-butyl perbenzoate, benzoyl
peroxide, methyl ethyl ketone peroxide,
2,5-dimethyl-2,5-di(tertiary-butylperoxy) hexane (Wallace and
Tiernan's Lupersol 101), 2,5-dimethyl-2,5-di(tertiary-butylperoxy)
hexyne-3 (Wallace and Tiernan's Lupersol 130) and the like. The
preferred peroxide is di-(tertiary-butyl) peroxide.
The metal catalyst used in the practice of this invention is a
heavy metal salt of a higher fatty acid which is soluble in the
chosen organic solvent. These salts are those commonly used as
driers in the paint, varnish, printing ink and linoleum industries
and have the formula
(RCOO).sub.x Me
wherein x represents the valence of the metal Me; Me is a metal of
the group consisting of cobalt, copper, zinc, aluminum, iron, lead,
manganese, calcium, barium, lithium, magnesium, or mixtures
thereof, and (RCOO--) is the residue of an organic aliphatic,
alicyclic or aromatic monocarboxylic acid having from about 7 to
about 24, preferably about 18, carbon atoms. (See Kirk-Othmer,
Encylcopedia of Chemical Technology, Second Edition, Volume 7
(1965), pp. 272-283).
Suitable metal salts include the cupric, zinc, cobalt, aluminum,
iron, manganese, calcium, barium, lithium or magnesium. Salts of
naphthenic, linoleic, linoresinic, palmitic, oleic, stearic,
lauric, rosin, tall oil, 2-ethylhexoic, 3,5,5-trimethylhexoic or
neodecanoic acids. The preferred metal catalyst salts are the
naphthenates, especially cobalt naphthenate.
The peroxide solution may be applied to the deposit to be treated
by any suitable procedure, e.g., spraying, dipping, brushing or the
like. In the practice of the present invention immersion for
prolonged periods of time is not necessary or desirable. The
peroxide solution or the active ingredients of the peroxide
solution, i.e., the peroxide and metal catalyst, are permitted to
remain in contact with the deposit for a short period of time
(e.g., 5 to 20 minutes) and the treated deposit is then heated to
accomplish scorching.
Heating is carried out for a period of from about 15 minutes to
about 4 hours at temperatures of from about 100.degree. to about
240.degree. Fahrenheit, preferably from about 160.degree. to about
220.degree. Fahrenheit. Of course, the time and temperature of the
heat treatment will vary with the deposit involved and the amount
thereof, the particular peroxide treatment solution used, and other
like factors. In almost all cases satisfactory results are achieved
with heating times of 1 hour or less.
The scorched deposit is subjected to the action of an aqueous
alkaline cleaning solution to remove it from the surface to be
cleaned. This removal step may be performed subsequent to or
simultaneously with the scorching step. Wherever possible the steps
are performed simultaneously, thus reducing the overall time
required to complete the overall removing process. The two steps
are conducted sequentially in the presently preferred embodiment of
the invention. It is to be understood, however, that simultaneous
performance of the scorching and removing steps has been
demonstrated to be operable and is thus included within the scope
of the invention.
The aqueous alkaline solution used in the final step of the present
invention can be a solution of an alkali metal hydroxide alone or
of a mixture of an alkali metal hydroxide with minor proportions
(e.g., from about 5 to about 30 weight percent of the total
alkaline solids) of one or more other alkaline salts such as alkali
metal carbonate, phosphate, metasilicate or the like. The working
solutions of alkali strippers will usually have a dissolved solids
concentration of about 5 to about 25 percent, preferably 10 to 20
percent by weight, corresponding roughly to about 0.5 to 3,
preferably 1 to 2, pounds of solids per gallon of water. However,
any alkaline cleaner which will leave a clean surface can be used
and the exact formulation is unimportant to the present invention
as long as the solution contains sufficient caustic soda or caustic
potash to provide a 2.0 to 50.0 percent (by weight) solution of
free caustic soda or caustic potash, as part of the dissolved
solids, any of the usual co-additives known in the prior art. Some
of the typical co-additives are disclosed, for example, in the
aforecited Volume 14 of Kirk Othmer Encyclopedia of Chemical
Technology, Second Edition.
The invention will be further understood from the following
illustrative, non-limiting examples.
EXAMPLE 1
In this Example the peroxide solution comprised 60 weight percent
kerosene solvent, 30 weight percent di-(tertiary-butyl) peroxide
and 10 weight percent cobalt naphthenate catalyst.
To demonstrate the present invention a 3 inch by 1 inch steel test
panel was coated with a Neoprene latex and the coating was allowed
to dry for 24 hours at room temperature. A film of the above
peroxide solution was sprayed on the Neoprene coating and the panel
was immediately immersed in a hot (200.degree. Fahrenheit) stripper
solution comprising 2.5 percent caustic potash, 1.8 percent
cresylic acid, 0.5 percent of a sequesterant and balance water. The
panel was retained in the hot stripper solution for 20 minutes
after which it was removed and permitted to cool to room
temperature.
The Neoprene coating was observed to be severely degraded and
partially stripped from the test panel at the time of removal from
the hot stripper solution. The Neoprene still remaining on the
panel was easily removed by manual stripping.
In a repeat of the foregoing procedure, equally good results were
obtained with a like peroxide solution in which the solvent was
orthodichlorobenzene instead of kerosene.
EXAMPLE 2
In this example the peroxide solution contained 63 weight percent
orthodichlorobenzene, 32 weight percent di-(tertiary-butyl)
peroxide and 5 weight percent cobalt naphthenate. The aqueous
cleaning solution contained 94.5 weight percent water, 2.5 weight
percent potassium hydroxide, 1 weight percent of a sequestrant and
2 weight percent couplers (i.e., water soluble or water miscible
cosolvents).
The test sample was a 3 inch by 1 inch steel panel coated with a
polyvinylacetate latex and dried at room temperature for 24 hours.
The panel was dipped briefly in the above peroxide solution, and
then allowed to drain for 10 minutes at room temperature. The panel
was then immersed in the above alkaline cleaning solution at
190.degree. Fahrenheit for 30 minutes.
Results were like those obtained in Example 1, with portions of the
polymer coating removed and the remainder badly degraded and
readily removed manually after removal of the test panel from the
hot aqueous cleaning solution.
When attempts were made to clean like test panels with the aqueous
alkaline cleaner solution alone, there were no signs of any kind of
attack or removal of the resinous deposit.
EXAMPLE 3
In this example the peroxide solution was the same as the one used
in Example 2 except for the substitution of tertiary-butyl
perbenzoate for the di-(tertiary-butyl) peroxide.
A portion of an automobile tire mold bearing a black film of cured
tire compound was dipped briefly in the peroxide solution and then
allowed to drain for 10 minutes at room temperature. The peroxide
treated piece was then heated in a hot air oven for 30 minutes at
120.degree. Fahrenheit.
After cooling to room temperature the piece was manually cleaned by
rubbing with a cloth in an aqueous solution of a mild dishwashing
compound. Some of the cured rubber compound remained in the mold
crevices but the accessible undesired deposits were removed.
Previous attempts had been made to remove this rubber deposit by
using mildly alkaline products, as well as water miscible solvent
products containing over 50 percent orthodichlorobenzene both with
and without the aid of ultrasonics. These attempts showed no effect
on the rubber deposit.
EXAMPLE 4
The peroxide solution was identical to the one used in Example 3.
The aqueous alkaline cleaning solution contained 3.0 weight percent
sodium hydroxide and 5.0 weight percent sodium carbonate, together
with other typical coadditives.
The substrate to be cleaned was a closed 6,000 gallon steel tank
coated with a thin film of a dried adhesive. The identity of the
adhesive was not known. The contaminated tank surface was sprayed
with one-half gallon of the peroxide solution and then heated with
steam under atmospheric pressure for 30 minutes. Immediately after
this heat treatment the coated tank surfaces were hit for 1 hour
with a pressurized spray (150 pounds per square inch gauge) of the
above alkaline cleaning solution pre-heated to 140.degree.
Fahrenheit.
The tank was completely clean after the foregoing treatment.
Previous attempts to clean the tank with the alkaline product alone
only served to further harden the coating of adhesive deposit and
render more difficult the hand scraping operations then in use.
* * * * *