U.S. patent number 3,692,884 [Application Number 04/797,691] was granted by the patent office on 1972-09-19 for phosphate esters.
Invention is credited to Edwin R. Gaskell.
United States Patent |
3,692,884 |
Gaskell |
September 19, 1972 |
PHOSPHATE ESTERS
Abstract
A novel group of compounds, the reaction product of an amine and
a phosphate ester that are useful as dispersing agents for the
finely divided metal oxides used in preparing magnetic tape
coatings. The compound having the formula: where R is a hydrocarbon
radical; A is an alkylene radical; R' is an amine; and the sum of
x, y and z is 3.
Inventors: |
Gaskell; Edwin R. (San Carlos,
CA) |
Family
ID: |
25171544 |
Appl.
No.: |
04/797,691 |
Filed: |
February 7, 1969 |
Current U.S.
Class: |
558/185; 544/157;
546/21; 558/114; 987/194; 987/224; 544/84; 544/337; G9B/5.274 |
Current CPC
Class: |
G11B
5/7013 (20130101); C07F 9/24 (20130101); C07F
9/091 (20130101) |
Current International
Class: |
C07F
9/00 (20060101); C07F 9/09 (20060101); C07F
9/24 (20060101); G11B 5/70 (20060101); C07f
009/08 (); C07f 009/22 () |
Field of
Search: |
;260/925,924,944,950,951,980,984,987 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
houben-Weyl, Methoden Der Organischen Chemie, Band XII/2 (1964) p.
401 and 402..
|
Primary Examiner: Rebold; Joseph
Assistant Examiner: Raymond; Richard L.
Claims
What is claimed is:
1. A composition of matter having the following formula:
wherein x and z are whole number integers of from 1 to 2, y is a
whole number integer of from 0 to 1, with the proviso that the sum
of x, y and z is 3;
R is a hydrocarbon radical of up to 30 carbon atoms, which is
aliphatic, alicyclic, aromatic or combinations thereof;
n is an integer of from 3 to 35;
A is an alkylene radical of from two to three carbon atoms;
R' is a monovalent radical of the formula:
-- NH(A'NH).sub.m H,
wherein A' is an alkylene radical of from two to three carbon
atoms; and
m is a whole number integer of from 0 to 5.
2. A composition according to claim 1 wherein A and A' are
ethylene, m is 0-3, n is 6-15 and R is an alkyl radical of from 10
to 20 carbons.
3. A composition according to claim 1, wherein m is 2, n is about 4
and R is dodecyl.
4. A composition according to claim 1, wherein m is 3, n is about 8
and R is pentadecyl.
5. A composition according to claim 1, wherein R is an
alkylaromatic radical of from 10 to 20 carbons, n is an integer of
from 6-15, and A and A' are ethylene radicals.
6. A composition according to claim 5, wherein m is 3, n is about
10 and R is nonylphenyl.
7. A composition according to claim 5, wherein m is 2, n is about
10 and R is nonylphenyl.
8. A composition according to claim 5, wherein m is 3, n is about
11 and R is octylphenyl.
9. A composition according to claim 5, wherein m is 0, n is about
10 and R is nonylphenyl.
10. A composition according to claim 5, wherein m is an integer of
from 2 to 3.
11. A composition according to claim 5, wherein m is 0.
Description
The use of a moving magnetic wire as a means for reproducing audio
signals was first demonstrated in 1898. However, it is only since
the late 1940's that theories, techniques, and materials have been
developed which make possible the reproduction of audio signals
with a satisfactory performance from the standpoint of frequency
range, signal-to-noise ratio, and distortion. Although satisfactory
performances have heretofore been obtained with magnetic wire,
magnetic tape consisting of a paper or plastic-base tape coated
with a thin layer of magnetized ferromagnetic powder such as iron
oxide, is now almost universally used in magnetic
sound-reproduction.
Such oxide coated tapes are generally employed in widths such as
one-quarter or one-half inch and utilized in rolls of up to about
2,500 feet. Information is recorded on a series of parallel tracks
extending the length of the tape. As this type of equipment has
become more sophisticated, the characteristics of the oxide coating
have become more critical. Thus, an accurate dispersion of the
metal oxide in the coating is now essential to uniformity of
reproduction. Various dispersing agents have heretofore been
employed to assist in providing such a uniform iron oxide coating
over the base tape; see for example U.S. Pat. No. 3,144,352 where
surfactants such as lecithin have been utilized for this
purpose.
The present invention is directed to a novel group of amine salts
of complex phosphate esters that have been found to be particularly
advantageous when employed for dispersing finely divided
ferromagnetic oxide particles, such as acicular gamma ferric oxide,
in tape-coating systems. These novel compounds are broadly
described by the following formula:
wherein x and z are integers from 1 to 2, y is an integer of 0 to 1
and the sum of x, y and z is always 3; R is a hydrocarbon radical
of up to 30 carbons that is selected from aliphatic, cyclic,
aromatic and combinations thereof; n is an integer from 3 to 25; A
is an alkylene radical of from two to three carbon atoms; R' is a
monovalent radical of from 0-20 carbons (preferably 0-12 carbons)
selected from aliphatic amines of the formula --NH(A'NH).sub.m H
and monocyclic heterocyclic compounds containing from one to three
nitrogen atoms and from zero to one oxygen atoms as the only
annular hetero atoms. The term aliphatic amines is intended to
include alkylene polyamines such as triethylene tetraamine,
diethylene triamine as well as ammonia. The term heterocyclic
compounds is intended to include morpholine, piperazine, pyridine,
triazine, pyrrole, pyrrolidine, and the like with and without
substituents.
IN the preferred embodiment the phosphate esters are of the
formula:
wherein R is an alkylaromatic radical of from 10 to 20 carbons such
as octyl- or nonylphenyl; A and A' are ethylene radicals; m is an
integer of from 2 to 3; n is an integer of from 6 to 15, more
preferably an average of 8 to 10; and y is 0 and x and z total 3.
Depending upon the extent of the reaction, any combination of up to
a total of three alkoxy and/or amino groups may be attached to the
pentavalent phosphorous atom, it being understood of course that at
least one alkoxy and at least one amino radical are always present
in the resulting composition.
The novel products of this invention are produced by a carefully
controlled two-step process wherein a long chain organic alcohol
such as alkylphenoxypoly(alkyleneoxy)alkanol is first reacted
(esterified) with, preferably, phosphorous pentoxide to form at
least a partial phosphate ester. Thereafter, the resulting mono- or
di- phosphate ester is reacted with the above-described amine
either through partial neutralization, or displacement of the ester
by the amine.
Briefly, in the 2-step reaction of this invention, a pentavalent
phosphorous such as phosphorous pentoxide (P.sub.2 O.sub.5), the
acid anhydride of phosphoric acid, or phosphorous oxychloride, in
an amount in excess of that theoretically required, is combined
with a high molecular weight nonionic surface active agent having
the general formula:
R (OA).sub.n OH (2)
wherein R, A, and n have the definitions set forth for formula (1),
above. The excess of pentavalent phosphorous is necessary to ensure
that no free surface active agent remains.
The product obtained from this esterification reaction is thought
to be primarily a mixture of the mono- and di-ester. The excess of
pentavalent phosphorous ensures that little, if any, tri-ester will
be formed. Thus the resulting compounds appear to be defined by the
formula:
wherein R, A, x and n have the definitions set forth with respect
to formula (1), supra.
Thereafter, and following the removal of the excess pentavalent
phosphorous, such as by filtering, the phosphate ester of formula
(3) is reacted with an amine having at least one nitrogen and
including from 0 to 20 carbon atoms. As previously discussed with
respect to formula (1) and (1a), the amine can be either aliphatic
or heterocyclic. Sufficient of the amine is introduced to adjust
the pH of the resulting amine salt to about 5 to 7. In the
preferred embodiment, the amine is aliphatic and an alkylene
polyamine defined by the following formula:
H NH(A' NH).sub.m H (4)
wherein A' and m have the definitions set forth for formulas (1)
and (1a), above.
The nonionic surface-active alcohols useful for reaction with the
acid anhydride of phosphoric acid include the ethylene oxide
adducts of the alkanols and alkylphenols. Such substances are
commercially available under trademarks such as Neodol, from Shell
Oil Company and Igepal, from General Analine and Film Corporation.
For purposes of convenience, reference will frequently be made in
the remainder of this specification to the use of Igepal CO-630, a
nonylphenoxypoly(ethyleneoxy)ethanol, as the surface active
alcohol. However other long chain
alkylphenoxylpoly(alkyleneoxy)alkanols such as Igepal CO-430,
Igepal CA-630 and the like, as well as
alkylpoly(alkyleneoxy)-alkanols containing up to about 25
alkyleneoxy units, are suitable.
Although the reaction conditions during formation of the phosphate
esters in the initial step are not particularly critical, it has
been found to be critical for the amount of amine employed to be
sufficient to adjust the pH of the resulting complex salt to the
range of about 5-7, and preferably 5-6. When the pH of the
resulting amine salt is substantially in excess of about 6, the
reactants become solid and hard to handle when introduced into the
ferromagnetic oxide coating composition. Furthermore, a pH lower
than about 5 inhibits subsequent dispersion of the metal oxide in
the coating system. During formation of the novel compounds of this
invention, the temperature conditions may vary over a wide range,
but it is desirable that the reaction temperature at no time
greatly exceed the boiling point of water at atmospheric pressure.
The reaction pressure employed can be either sub-atmospheric or
super-atmospheric, in addition to ambient.
The novel dispersing agents of this invention can be incorporated
with any of the iron oxide-containing systems presently employed in
the magnetic tape production industry. Such systems have heretofore
been prepared with iron oxide as well as various other components
normally incorporated in the binder system, including resin
materials, lubricants, and solvents, such as set forth in U.S. Pat.
No. 3,144,352, supra. For this reason, the present invention is not
intended to be limited to any particular metal oxide system, but is
useful whenever uniform dispersion of the metal oxide is desirable.
The amount of dispersing agent employed can vary widely, as little
as about 1 percent by weight being suitable, while amounts up to 10
percent can be advantageous. It is preferable to use from about 2-5
percent based on the total weight of the coating composition.
The resulting coating incorporating the novel dispersing agent of
this invention can be employed with a wide variety of known tape
bases. However, it will be appreciated by those skilled in the art
that tapes formed of polyesters such as polyethylene terephthalate,
and available under the trade name Mylar, are particularly suitable
as they have an extremely long life.
The organophosphorous compounds, resulting from the reaction of the
long chain alcohol with the pentavalent phosphorous oxides, depend
upon both the extent to which the esterification reaction is
allowed to continue and the relative concentration of the
reactants. Subsequently, the amount of amine displacement (or
neutralization) will again depend upon the amount of reactants
present as well as upon the actual reaction conditions. As
previously set forth it is only critical that at least one alkoxy
and one amino radical remain complexed with each pentavalent
phosphorous. Suitable solvents include toluene and tetrahydrofuran
among the many others that could be utilized.
To further illustrate the invention, the following examples are
provided. It should be understood that the particular details of
the examples are not to be regarded as limitations as they may be
varied, as will be understood by one skilled in this art.
EXAMPLE I
Igepal CO-630, a nonylphenoxypoly(ethyleneoxy)ethanol, in an amount
of about 1,000 grams was heated with agitation to about 150.degree.
F. Phosphorous pentoxide in an amount of about 96 grams was slowly
added while the reaction temperature was allowed to rise to about
180.degree. F. The phosphorous pentoxide was added at a rate
sufficient to maintain the temperature in the range of 170.degree.
to 190.degree. F during the addition which took about 1 hour. The
rate of addition was decreased as the reaction neared completion.
The reaction temperature was retained at about 180.degree. F for
about 1 hour after the addition of the phosphorous pentoxide. Some
phosphorous pentoxide remained unreacted in the clear liquid
portion. The resulting ester was filtered through diatomaceous
earth. Other filters having a 50-75 micron porosity are also
suitable for this filtering operation. Care was taken to dispose of
the filtering medium as the free phosphorous pentoxide presented a
fire hazard.
500 grams of the resulting phosphate ester were combined with 550
grams of toluene and heated to approximately 200.degree. F.
Triethylene tetraamine, in an amount of 50 grams was added slowly
to avoid raising the temperature of the reaction to above
225.degree. F. The resulting amine salt of the complex phosphate
ester was filtered and found to have the following characteristics:
The viscosity was found to be about 100-200 centapoise and the
composition had a weight of about 8.2 pounds per gallon. The acid
number was found to be in the range of 50-60 and the pH of a 1
percent aqueous solution of the complex ester was found to be
between about 5 and 7.
EXAMPLE II
Utilizing 30 parts of the complex ester formed in example I, above,
in lieu of 30 parts of lecithin, the coating composition set forth
in example I of U.S. Pat. No. 3,144,352 is prepared. The coating is
applied to a Mylar tape, and the dispersion characteristics of the
iron oxide in the coating are found to be excellent.
Although the foregoing invention has been described in some detail
by way of illustration and example for purposes of clarity of
understanding, it will be appreciated that certain changes and
modifications may be practiced within the scope of the invention as
limited only by the scope of the appended claims.
* * * * *