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Description  |
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BACKGROUND OF THE INVENTION
This invention relates to a catalytic process for preparing novel
hydrocarbonaceous polymeric type compounds. In particular, this invention
provides a new catalytic process for producing hydrocarbonaceous polymeric
compounds by reacting one hydrocarbonaceous compound possessing an
isonitroso group with a second compound possessing a cyclic ether group.
This invention further relates to novel O-polyalkoxylated and substituted
O-polyalkoxylated high molecular weight alkanone oximes. Moreover, this
invention provides a new catalytic process for producing O-polyalkoxylated
high molecular weight alkanone and alkanal oximes by the reaction of an
oxirane with paraffin oximes.
An object of this invention is to provide a new catalytic process for
preparing novel polymeric type materials.
Another object of this invention is to provide a novel catalytic process
for preparing hydrocarbonaceous polymeric compounds.
Another object of this invention is to provide a novel catalytic process
for preparing polymeric type materials of improved purity and color.
Yet another object of this invention is to provide a process for preparing
novel surfactant compounds valuable as nonionic biodegradable detergents.
Other objects and advantages will become apparent from a reading of the
following detailed description and examples.
SUMMARY OF THE INVENTION
Broadly, this invention contemplates a catalytic process for preparing a
novel hydrocarbonaceous polymeric compound which comprises contacting in
the presence of a basic nitrogen catalyst a first hydrocarbonaceous
compound possessing an isonitroso group with from 2 to 40 moles of a
second hydrocarbonaceous compound possessing a cyclic ether group per mole
of said first compound in the substantial absence of water. The first
hydrocarbonaceous compound possessing an isonitroso group contemplated
herein is a paraffin oxime and the second hydrocarbonaceous compound
possessing a cyclic ether group contemplated herein is an oxirane as
defined below.
In particular, this invention contemplates a process for preparing novel
O-polyalkoxylated high molecular weight alkanone and alkanal oximes which
comprises contacting a paraffin oxime having at least 6 and preferably at
least 10 carbon atoms with a basic nitrogen catalyst and from 2 to 40
moles of an oxirane per mole of paraffin oxime in the substantial absence
of water.
The O-polyalkoxylated high molecular weight alkanone and alkanal oximes
prepared by our process correspond to the formula:
##EQU1##
where R and R' are hydrogen or alkyl groups having from 1 to 11 carbon
atoms or where R and R' together may form a polymethylene radical and
where the sum of R and R' equals at least 5 and preferably at least 9,
carbon atoms and up to 22 carbon atoms, preferably the sum equals from 9
to 12 carbon atoms, where R" and R'" are hydrogen, alkyl groups having
from 1 to 5 carbon atoms, cycloalkyl or aryl groups having from 6 to 20
carbon atoms and where x equals from 2 to 40 and suitably from 3 to 40. In
highly preferred embodiments x is from 6 to 15. Contemplated within the
scope of this invention are mixtures of O-polyalkoxylated high molecular
weight n-alkanone and n-alkanal oximes where such compounds are prepared
from mixtures of C.sub.10 to C.sub.13 or higher n-paraffin oximes.
Illustrative of O-polyalkoxylated high molecular weight n-alkanone oximes
prepared according to the instant invention we mention
O-5'-hydroxy-3'-oxapentyl 2-decanone oxime, O-5'-hydroxy-3'-oxapentyl
2-undecanone oxime, O-8'-hydroxy-2', 5', 8',-trimethyl-3', 6'-dioxaoctyl
6-undecanone oxime, O-8'-hydroxy-2', 5', 8'-triphenyl-3', 6'-dioxaoctyl
6-undecanone oxime, O-17'-hydroxy-3', 6', 9', 12', 15'-pentaoxaheptadecyl
(C.sub.10 -C.sub.13)-n-alkanone oxime and O-26'-hydroxy-3', 6', 9', 12',
15', 18', 21', 24'-octaoxahexacosyl (C.sub.10 -C.sub.13)-n-alkanone oxime.
As O-polyalkoxylated high molecular weight n-alkanal oximes we include
O-17'-hydroxy-3', 6', 9', 12', 15'-pentaoxaheptadecyl (C.sub.10
-C.sub.13)-n-alkanal oxime and O-26'-hydroxy-3', 6', 9', 12', 15', 18',
21', 24'-octaoxahexacosyl (C.sub.10 -C.sub.13)-n-alkanal oxime. Products
derived from cyclic oximes include O-5'-hydroxy-3'-oxapentyl cyclohexanone
oxime and O-26'-hydroxy-3', 6', 9', 12', 15', 18', 21',
24'-octaoxahexacosyl cycloheptanone oxime.
According to this invention the contemplated oximes are derived from normal
and cyclic paraffin oximes having at least 6 or at least 10 and up to 23
carbon atoms and preferably from 10 to 13 carbon atoms. Included as
starting material we mention 2-hexanone oxime, cyclohexanone oxime,
cycloheptanone oxime, 2-octanone oxime, 2-decanone oxime, 3-decanone
oxime, 4-decanone oxime, 5-decanone oxime, 2-undecanone oxime,
3-undecanone oxime, 4-undecanone oxime, 5-undecanone oxime, 6-undecanone
oxime, 2-dodecanone oxime, 4-dodecanone oxime, 6-dodecanone oxime,
2-tridecanone oxime, 3-tridecanone oxime, 5-tridecanone oxime,
7-tridecanone oxime, undecanal oxime, dodecanal oxime and tridecanal oxime
along with mixtures thereof. In general, the paraffin oximes correspond to
the formula:
##EQU2##
where R and R' are as defined above. Such illustrative paraffin oximes
contemplated as starting materials and listed above may be prepared, for
example by photochemically reacting in a light transmittable reaction
vessel a paraffin having 6 or 10 or more carbon atoms and up to 23 carbon
atoms or a mixture of paraffins having 10 to 13 or more carbon atoms with
a gaseous nitrosating agent such as nitrosyl halide, nitrosyl sulfuric
acid or a mixed nitrosating agent such as nitric oxide and chlorine under
a nitrosating agent partial pressure of at least 125 mm Hg. Further, the
photochemical reaction is conducted under the influence of light excluding
wave-lengths below 200 millimicrons such that high molar yields of oxime,
up to 92% or higher, may be realized. Reaction temperatures of from
32.degree. to 110.degree.F. have been found to be applicable and the
conversion product comprises approximately 95% of the n-paraffin oxime
salt of, for example, hydrochloric acid which in turn is converted to the
paraffin oxime by neutralization with a base such as aqueous ammonia or
caustic soda. Separation of the oxime during neutralization is materially
aided by employing a low boiling hydrocarbon exemplified by cyclohexane
and pentane such that inorganic salts of neutralization are carried along
in an aqueous phase with the low boiling hydrocarbon carrying along with
oxime. The oximes may be recovered subsequently by evaporation of the
hydrocarbon. The illustrative procedure described above for preparing
normal paraffin oximes is described in U.S. Pat. No. 3,578,575 assigned to
the assignee hereof and is hereby incorporated by reference.
Alternatively, the paraffin oxime may be prepared by any of the widely
known classical procedures. In particular, oxime preparation by the
reaction of alkanals and alkanones with hydroxylamines under appropriate
conditions is generally applicable.
More specifically, the process of this invention comprises reacting a
paraffin oxime, as hereinabove provided and defined, with an oxirane in
the presence of a basic nitrogen catalyst that include basic nitrogen
compounds illustrated by amines such as triethylamine, diethylmethylamine
and dimethylethylamine. The catalysts contemplated in the instant
invention are tertiary nitrogen compounds corresponding to the formula:
##EQU3##
where R, R.sup.1 and R.sup.2 are alkyl, cycloalkyl or aryl groups or where
R, R.sup.1 and/or R.sup.2 together with the nitrogen (N) are heterocyclic
and where R, R.sup.1 and R.sup.2 are from 1 to 12, preferably from 1 to 6,
carbons, and where the sum of R, R.sup.1 and R.sup.2 is from 3 to 36.
Illustrative of the tertiary nitrogen compounds we mention tertiary
aliphatic, alicyclic and aromatic amines including N-butyldidodecylamine,
N,N-diethylallylamine, N,N-diethylcyclohexylamine,
N,N-diethyldodecylamine, N,N-dimethylallylamine, N,N-dimethylbenzylamine,
N,N-dimethyltertbutylamine, N,N-dimethyloctylamine,
N,N-diisopropylethylamine, N,N-dimethylethylamine, N,N-diethylmethylamine,
N,N-dimethylpropylamine, N,N-diethylpropylamine,
N,N-ethylmethylpropylamine, N-ethyldibenzylamine, tributylamine,
tridodecylamine, triethylamine, trihexylamine, trimethylamine,
tricyclohexylamine, triisopropylamine and triphenylamine. Heterocyclic
compounds contemplated include pyridine, methylpiperidine,
2-ethylpyridine, 1,4-dimethylpiperazine, 4-ethylpyridine, 2,4-lutidine,
3-picoline, 2,4,6-trimethylpyridine and quinoline. The preferred catalysts
are triethylamine, pyridine, methylpiperidine, N,N-dimethylethylamine,
N,N-diethylmethylamine, N,N-dimethylpropylamine, N,N-diethylpropylamine
and N,N-ethylmethylpropylamine. Highly preferred catalysts are
trialkylamines of the group triethylamine, diethylmethylamine and
dimethylethylamine.
In practice, the paraffin oxime is contacted with catalytic amounts of the
basic nitrogen compound, generally in amounts of from 0.001 to 5.0,
preferably 0.08 to 2.0, moles of catalyst per mole of paraffin oxime. The
catalyst and oxime are intimately mixed in an inert atmosphere whereby
trace amounts of water are eliminated from the system as by purging the
system with an inert gas such as dry nitrogen at about 100.degree.C. or at
reduced pressure and at a correspondingly reduced temperature. Preferably,
the catalyst and oxime are purged with an inert gas prior to heating the
reaction mixture so as to avoid partial removal of the catalyst by gas
purging. In practice, the oxime charged should be essentially anhydrous
when charged to the reactor. Thereafter the oxirane is added to the
substantially anhydrous environment such that 2 to 40, suitably 3 to 40
and preferably from 6 to 40 moles of oxirane are added per mole of
paraffin oxime, at a rate of from 0.01 to 5 moles per hour of oxirane per
mole of paraffin oxime. In a highly preferred embodiment 6 to 15 moles of
oxirane are added per mole of paraffin oxime. Appropriate reaction
temperatures range from about 0.degree. to 300.degree.C., generally
0.degree. to 200.degree.C., suitably 20.degree. to 160.degree.C. and we
prefer to conduct the reaction at from about 40.degree. to 90.degree.C.,
under pressures ranging from sub-atmospheric to 100 p.s.i.g. The reaction
time is normally between 1 and 24 hours although longer and shorter
periods may be employed.
The oxiranes contemplated as starting materials correspond to the formula:
##EQU4##
where R" and R'" are as previously defined. Illustrative of the materials
falling within the above formula we mention oxirane (ethylene oxide),
methyloxirane, ethyloxirane, 2,3-dimethyloxirane, phenyloxirane,
2-methyl-3-phenyloxirane and cyclohexyloxirane.
An important aspect of this invention centers about conducting the reaction
in the substantial absence of water. To successfully provide the
designated O-polyalkoxylated high molecular weight alkanone and alkanal
oximes in high yields with minimal amounts of polyalkylene glycols, a
substantially anhydrous reaction medium is necessary such that water is
present in an amount not exceeding 0.5 weight percent, and preferably not
exceeding 0.1 weight percent. The presence of substantial amounts of water
cause the oxirane to form polyethylene glycols. Moreover, it is
particularly beneficial to employ catalysts having a water content less
than 0.1 weight percent as the same results in reduced glycol formation.
Catalysts possessing water contents in excess of 0.1 weight percent can be
treated with for example potassium hydroxide or 4A molecular sieves so as
to reduce their water content to less than 0.1 weight percent prior to
using the same in the instant process. The treatment of the catalyst with
either potassium hydroxide or 4A molecular sieves consists simply of
mixing the catalyst therewith. The treatment of for example amines with
potassium hydroxide pellets is the classical drying technique and the use
of 4A sieves to remove water is described in Adams and Johnson, Laboratory
Experiments in Organic Chemistry, Fourth Edition, The Mac Millan Company,
pages 121-122. However, the desired characteristics and uses of the
product will govern the permissible level of water within the limits
specified above and ultimately the amount of glycol in the product.
While such non-aqueous environments as dioxane and tetrahydrofuran may be
employed as reaction diluents, we in fact prefer to undertake the reaction
of the paraffin oxime and the oxirane in the absence of added diluents. In
a preferred embodiment the reactants themselves, particularly excessive
amounts of catalyst such as triethylamine, dimethylethylamine,
diethylmethylamine, etc., constitute the reaction medium. In contrast to
the use of other materials as catalysts for the instant reaction such as
sodium hydroxide, sodium ethoxide, lithium ethoxide and the like, the use
of the tertiary nitrogen compounds function effectively as both catalyst
and diluent. This is highly advantageous inasmuch as the nitrogen
compounds particularly those of lower molecular weight contemplated as
catalyst herein can be easily recovered from the reaction products by
stripping and recycled for further use, whereas alkali catalysts require
the use of tedious neutralization and product purification procedures. The
higher molecular weight catalysts can be recovered by thin film
distillation.
Moreover, the reaction medium may be composed of mixed C.sub.10 to C.sub.13
normal paraffin oximes along with mixtures of oxiranes. In another
embodiment, the precursor paraffin oximes are provided as a crude oxime
starting material such that the material contains from 90% and higher
paraffin oximes along with lesser amounts of ketones. When operating with
crude oximes starting materials, the polyalkoxylated higher molecular
weight alkanone or alkanal oxime product is recovered in high purity and
yield by employing such techniques as thin film evaporation of the
reaction product such that ketones, unreacted oximes and low molecular
weight monoalkoxylated or polyalkoxylated oximes are removed. Thin film
evaporation, utilizing for example a Turba-Film Processor, is accomplished
by distributing the product on the heated walls of an evaporator such that
low boiling compounds are quickly vaporized and condensed. Short residence
times are customarily employed to minimize product decomposition. In
practice, the weight percent recovery of the final product has exceeded
90% and is in most instances 98% or better.
An unexpected benefit derived from the use of the instant basic nitrogen
catalysts is the lighter burgundy color possessed by the polyalkoxylated
oximes as opposed to the dark colored product recovered after the
utilization of alkali catalysts. Another advantage of the instant process
is that the product contains less ketone contaminants or by-products than
processes employing alkali catalysts.
In a further embodiment of this invention, the color of the instantly
produced polyalkoxylated oximes can, if desired, be altered to a shade of
yellow. This is accomplished by treating the crude product with a mild
oxidizing agent such as hydrogen peroxide, alkali hypochlorites or alkali
hypobromites and alkaline earth hypochlorites or alkaline earth
hypobromites such as sodium hypochlorite, potassium hypochlorite, sodium
hypobromite, potassium hypobromite, calcium hypochlorite, magnesium
hypochlorite, calcium hypobromite or magnesium hypobromite. Generally
decolorization of the oxime is undertaken by treating with an aqueous
solution of the oxidizing agent at a temperature of from about 0.degree.
to 300.degree.F., preferably from about 50.degree. to 150.degree.F., so as
to minimize ketone formation. Appropriate mole ratios of oxidizing agent
to polyalkoxylated oxime range from 0.05:1 to 3.0:1 and we prefer to use
ratios of 0.1:1 to 2.0:1. Depending upon the ultimately desired product
color and purity, the treatment with the aforementioned oxidizing agents
can be accomplished under a broad range of temperature conditions. In
general, weaker solutions of oxidizing agent, for example 5 percent
solutions, are employed at the higher temperatures whereas stronger
aqueous solutions, such as 30 percent, are utilized at the milder
treatment temperatures for periods of several minutes to 2 hours. In
applications where the oxime product is not a critical factor,
decolorization of the same may be omitted.
The novel polyalkoxylated high molecular weight alkanone and alkanal oximes
prepared according to the instant invention are useful as biodegradable
nonionic surfactants and detergents, and chemical intermediates in the
production of anionic detergents. These products are also useful as
lubricating oil additives and as anti-rust and anti-icing additives in
fuels.
Polyethoxylated C.sub.10 -C.sub.13 oximes exhibit detergency properties
generally similar to other polyethoxylated compounds containing similar
hydrophilic groups. When agitated in water the polyethoxylated C.sub.10
-C.sub.13 oximes produce voluminous amounts of foam that subsequently
requires several water rinses for complete removal. The formation of
stable emulsions of water, mineral oil and polyethoxylated oximes further
demonstrates the utility of these compounds as detergents. Moreover, the
polyalkoxylated oximes recited herein where the value of X in the formula
is 3 or higher possess solubility in water and are distinguishable over
monomeric type compounds where X has a value of 1 where the latter are
essentially insoluble in water. Water solubility represents an important
property insofar as the utility of these compounds as detergents is
concerned.
In order to more fully illustrate the nature of our invention and manner of
practicing the same the following examples are presented.
EXAMPLE I
22.981 Kilograms of mixed C.sub.10 -C.sub.13 n-paraffins were charged to a
photoreactor and reacted with nitrosyl chloride under the influence of
light excluding wavelengths below 200 millimicrons at 60.degree.F. The
gaseous NOCl and HCl was charged at the rate of 1.64 grams per minute and
at 0.95 grams per minute respectively, to produce crude oximes at the rate
of 1.83 grams per minute. After separation of the crude oxime acid salt,
the acid was neutralized with aqueous ammonia and the crude C.sub.10
-C.sub.13 oxime was separated. The molar selectivity to crude oximes was
87.4% with an overall recovery of 90.7 weight percent. The crude oxime
product contained 4-5 weight percent C.sub.10 -C.sub.13 ketones.
A 500 gram sample of crude C.sub.10 -C.sub.13 oximes prepared according to
the above procedure was mixed with 50.0 grams of anhydrous Na.sub.2
CO.sub.3 at 100.degree.C. for 4 hours. After cooling, the mixture was
diluted with 1.0 liter of acetone and filtered. The acetone was removed
from the filtrate under vacuum to yield an oxime product (428.0 grams)
containing less than 1.0 weight percent ketone. Continuous thin film
distillation of the treated oxime at 95.degree. to 115.degree.C. at 0.05
to 0.1 mm Hg pressure yielded a light yellow colored oxime.
234 grams (1.25 mole) of purified oxime as prepared above and 100 grams of
triethylamine (0.99 mole) were charged to a 2 liter reactor and heated to
145.degree.F. after purging the reactor with nitrogen. Ethylene oxide
(oxirane), 503 grams (11.4 moles), was charged to the reactor at an
average rate of 114.2 grams per hour under a reactor pressure of 0 to 30
p.s.i.g. while maintaining the temperature at 140.degree. to 155.degree.F.
After removal of triethylamine in vacuo, 718 grams of a light burgundy
colored product was recovered.
The product was treated with 5.6 weight percent basis the product of a 15
weight percent hydrogen peroxide solution at 70.degree. to 75.degree.F.
for one-half hours. After saturation with sodium chloride, the peroxide
treated product was extracted twice with equal volumes of chloroform.
After removal of the chloroform under vacuum, the product identified as
O-26'-hydroxy-3', 6', 9', 12', 15', 18', 21',
24'-octaoxahexacosyl-(C.sub.10 -C.sub.13)-n-alkanone oximes possessed as
ASTM color of less than 3.0. The detergency properties of this product was
determined using cotton fabric and a one percent stock solution. The
detergency test resulted in an outstanding detergency coefficient of 156
for the instant product as opposed to a coefficient of 100 for a
commercially available standard detergent.
EXAMPLE II
Purified C.sub.10 -C.sub.13 oximes, 187.0 grams (1.0 mole) prepared as in
Example I, 50 grams of triethylamine and 100 grams of cyclohexane
previously dried over a 4A molecular sieve were charged to a 2 liter
stirred reactor and reacted with 268 grams (6.1 moles) of ethylene oxide
(oxirane) at 145.degree.F. after purging the reactor with nitrogen in the
manner described in Example I. After removal of the triethylamine and
cyclohexane under vacuum, 586 grams of a burgundy colored product was
obtained. Treatment of the product with hydrogen peroxide in accordance
with the procedure set out in Example I yielded a light yellow colored
product designated O-17'-hydroxy-3', 6', 9', 12', 15'-pentaoxaheptadecyl
(C.sub.10 -C.sub.13)-n-alkanone oximes. The detergency test as in Example
I resulted in an outstanding detergency coefficient of 166.
EXAMPLE III
Purified C.sub.10 -C.sub.13 oximes, 187.0 grams (1.0 mole) prepared as in
Example I, 100 grams of triethylamine and 400.0 grams (9.1 moles) of
ethylene oxide (oxirane) were reacted in the manner described in Example
I. After removal of the triethylamine under vacuum, 587 grams of product
were recovered. The elemental analysis based on weight percent found:
carbon 57.50, hydrogen 9.85, nitrogen 2.90, oxygen 29.75 and C.sub.10
-C.sub.13 ketones 6.5. The product identified as O-26'-hydroxy-3', 6', 9',
12', 15', 18',21', 24'-octaoxahexacosyl-(C.sub.10 -C.sub.13)-n-alkanone
oximes possessed as ASTM color of 7.5 (burgundy) and a detergency
coefficient of 183.
EXAMPLE IV
Crude C.sub.10 -C.sub.13 oxime, 187.0 grams (1.0 mole), prepared as in
Example I, and 101 grams (1.0 mole) of triethylamine were charged to a 2
liter reactor and heated to 140.degree.F. after purging with nitrogen. 399
grams (9.07 moles) of ethylene oxide (oxirane) were charged to the reactor
at an average rate of 69.4 grams per hour under a reactor pressure of 30
p.s.i.g. A dark colored product, 575 grams, recovered after removal of
triethylamine under vacuum. The product possessed a detergency coefficient
of 170.
EXAMPLE V
The dark product of Example IV (100 grams) was treated with a mixture of 30
percent hydrogen peroxide and 10 grams of deionized water at 75.degree. to
110.degree.F. for 30 minutes. After treatment the mixture was saturated
with ammonium chloride and extracted with two volumes of chloroform. The
chloroform extract yielded 88.0 grams of a light orange colored product
having a detergency coefficient of 150 after filtration and removal of the
chloroform under vacuum.
EXAMPLE VI
Varying quantities of 2-undecanone oxime, trimethylamine and ethylene oxide
indicated below in Table I were charged to a 2 liter reactor and reacted
at 145.degree.F. under 0 to 30 p.s.i.g. as described in Example I.
TABLE I
______________________________________
A B C
______________________________________
2-Undecanone oxime wt., gms
111 111 111
Triethylamine wt., gms
100 100 100
Ethylene oxide wt., gms
84 164 241
Oxirane/oxime mole ratio
3.18 6.22 9.14
______________________________________
Product analysis of nuclear magnetic resonance identified each product as:
A - o-8'-hydroxy-3', 6'-dioxaoctyl 2-undecanone oxime
B - o-17'-hydroxy-3', 6', 9', 12', 15'-pentaoxaheptadecyl 2-undecanone
oxime
C - o-26'-hydroxy-3', 6', 9', 12', 15', 18', 21', 24'-octaoxahexacosyl
2-undecanone oxime
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