Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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BACKGROUND OF THE INVEi~IO~
This invention relates to the preparation of reaction
products of epoxides with organic compounds having an active
hydrogen and, more particularly, to a process for preparing
condensation reaction products of an epoxide and organic
compound having an active hydrogen with a restricted
molecular weight distribution and reduced by-products.
A variety of products such as surfactants, functional
fluids, glycol ethers, polyols, and the like are commercially
prepared by the condensation reaction of epoxides with
organic compounds havin~ an active hydrogen, generally in
the presence of an alkaline or acidic catalyst. The types
of products prepared and properties thereof depend on the
active hydrogen compound, the epoxide, and the number of
moles of epoxides employed as well as the catalyst, a mixture
of condensation products species being obtained containing
different molecular proportions of epoxide. Thus, the
reaction products generally obtained have a wide range of
molecular weights and of molecular distribution of the
epoxide units.
It is generally desirable to restrict the molecular
distribution of the mixture to adjacent analogues of the
desired product, insofar as possible, but this is quite
difficult to control. Acidic catalysts tend to give a
narrower molecular distribution than alkaline catalysts, but
also contribute to the formation of undesired by-products.
Thus, alkaline catalysts are generally used as the more
efficient type of catalyst but the molecular distribution in
the resulting products are more diffuse.
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12,337
Heretofore, several methods have been suggested for
providing reaction products of an active hydrogen compound
and epoxides having a narrower range of molecular weights
and molecular distribution of the epoxide unitsj or which
reduce or eliminate the production of undesirable poly(alkylene
glycol) and cyclic and straight chain ether by~products. For
example, in U. S. Patent 4,112,231 to Weibull et al it is
disclosed that the use of certain neutral inorganic fluoborate
and perchlorate salts will catalyze the reaction of
epoxides with active hydrogen compounds to give products having
a narrower molecular distribution and a larger proportion
of desired species; in V. S. Patent No. 3,682,849 to
Smith et al. improved ethoxylated derivatives of
Cll - C18 alcohols are prepared by removing unreacted
alcohol and lower ethoxylates from the conventionally
producted ethoxylate mixture using vapor phase separation
techniqu s; in IJ. S. Patent 2,870,220 to Carter, a two-stage
process is disclosed for preparing monoalkyl ethers of
ethylene glycol and polyethylene glycols of more restricted
molecular weight range wherein an alkanol and ethylene oxide is
reacted in the presence of an acidic catalyst during the first-
stage and then in the second-stage, after removal of acid
catalyst and unreacted alkanol, reacting the mixture with
ethylene oxide in the presence of an alkali metal alcoholate
of the initial alkanol; and in U.K. Patent 1,501,327 to
Laemmle et al is disclosed a method of preparing mono- and
poly-glycol ethers substantially free of undesired alkylene
glycol by-products which involves heating a reaction mixture
containing an alkylene oxide and an alcohol in the presence
of a catalyst containing alkali or alkaline earth cationh
wherein some or all of the catalyst is an anhydrous hish
1~7~6~ 12,337
boiling liquid residue prepared by concentrating the liquid
residue left from the same or similar etherification process
after removsl of the glycol ether product from the reaction
mixture. To the best of our knowledge, however, none of the
processes or special catalysts disclo~ed in the art are com-
pletely satisfactory in that they require multi-stage pro-
cedures or special acid-resistant equipment, give undesirable
by-products or simply do not provide sufficient control over
the molecular weight distribution. It would be highly
desirable, therefore, to develop a process wherein the
reaction of an epoxi~e with an organic compound having an
active ~ydrogen could be more readily carried out to prepare
products that have a narrow molecular weight distribution of
anologue species and contain only small amounts, at most,
of undesirable poly(alkylene glycol) and ether by-pro~ucts.
SUMMARY OF THE INVENTION
-
In accordance with the present invention there is provided
an improved process for the reaction of an organic compound
having an active hydrogen selected from the group consisting
of monohydric alcohols,phenols, polyols, mono- and dicarboxylic
acids, and amines with an epoxide which comprises carrying
out the reaction at a temperature at which the reaction
proceeds in the presence of at least a catalytic amount of
a basic salt of an alkaline earth metal selected from the
group consisting of calcium, strontium, barium, and mixtures
of the same which is soluble in the reactants and the
reaction products or of a compound of an alkaline earth
metal selected from the group consisting of calcium,
strontium, barium, and mixtures of the same which is
convertèd to the soluble basic ~alt thereof in situ.
~ 6~ 12,337
It has been discovered that soluble basic salts
of the alkaline earth metals hereinabove described not only
catalyze the reaction but also favor a narrower molecular
distribution, i.e., a more limited range of molecular species
and a lar~er proportion of the desired species in the reac-
tion product. ~loreover, the process of the invention can
be carried out in a single stage without the need for special
acid-resistant equipment and the products produced thereby
have been found, in general, to contain only small amounts
of undesired poly(alkylene glycol) and ether by-products.
DESCRIPTION OF THI: INVENTI~
_
In the process of the invention, an organic com-
pound having an active hydrogen selected from the group con-
sisting of monohydric alcohols, phenols, polyols, mono and
~icarboxylic acids, and amines is reacted with an epoxide
in the presence of a catalytic amount of a basic salt of
an alkaline earth metal selected from the grou? consisting
of calcium, strontium~ barium and mixtures of the same
which is soluble in the reactants and the reaction
products, or of a compound of an alkaline earth metal
selected from the group consisting of calcium, strontium,
barium and mixtures of the same which is converted to
the basic salt thereof in situ in the reaction mixture.
The reaction may be conducted in a conventional
manner, that is, the active hydrogen compound and the cata-
lyst are placed in a reactor, epoxide is added at the reac-
tion temperature until the desired number of moles which
may be from about 1 to about 30 or more moles of epoxide
per mole of active hydrogen compound have been added, and
the product is removed from the reactor and neutralized.
6 ~ ~
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The reaction may be conducted in the presence
of a solvent, but usually a solvent is not employed.
The temperature at which the reaction proceeds
is not narrowly critical and generally products can be
made at a reasonable rate of reaction and without
decomposition of the product at a temperature between
about 50~C and 270C with a temperature between about
100C and 200C being generally preferred. While the
pressure of the reaction is not narrowly critical, when
low-boiling epoxides such as ethylene oxide and propylene
oxide are employed,a pressurized reactor is preferably
used.
The product made may be neutralized with any
acid that will convert the catalyst to a neutral salt,
asfor example, acetic acid, carbon dioxide, sulfuric acid,
phosphoric acid and phenol.
Organic compounds hav~ng an active hydrogen
atom to which the present invention is applica~le may be
monohydric alcohols, phenols, polyols, mono- and dicarboxylic
acids, and amines.
The monohydric alcohols can be primary and
secondary aliphatic alcohols which are straight or
branched chain and have from one to about thirty carbon
atoms. Exemplary of such primary straight chain
monohydric alcohols are methanol, ethanol, butanol,pentanol,
hexanol, heptanol, octanol, nonanol, decanol, undecanol,
dodecanol, tridecanol, tetradecanol, pentadecanal,
hexadecanol, and octadecanol; and of such branched chain
or secondary alcohols are isopropyl alcohol, 2-ethylhexanol,
6.
~s'~6~
12,337
sec-butanol, iso-butanol, 2-pentanol, 3-pentanol,
iso-octanol, sec-octanol, and isodecanol. Particularly
suitable are linear and branched primary alcohols
and alcohol mixtures such as are pro~uced by
the "Oxo" reaction of normal C3 - C20 olefins
The process of the invention is also applicable
to cycloaliphatic monohydric alcohols, including for
example, cyclohexanol, cyclopentanol, cycloheptanol,
cyclopropanol and cyclooctanol, as well as phenyl-
substituted nonohydric alcohols such as benyzl alcohol,
phenylethyl alcohol, and phellylpropyl alcohol.
Applicable phenols include, for example phenol,
alkyl phenols such as p-methylphenol, p-ethyl phenol,
p-hutyl phenol, p-heptyphenol, p-nonyl phenol, dinonyl
phenol, p-decylphenol and the like. The aromatic
radicals may contain other conventional substituents
such as halide atoms.
The polyols to which the present invention is
applicable can have from two to thirty carbon atoms
2Q and from two to six hydroxyl groups including, for
example, glycerine, glycols such as ethylene glycol,
propylene glycol, butylene glycol, pentylene glycol,
hexyl~ne glycol, heptylene glycol, neopentylene glycol,
decylene glycol, diethylene glycol, triethylene glycol,
propylene glycol, dipropylene glycol, tripropylene glycol,
pentaerythritol, galactitol, sorbitol, mannitol,
erythritol, trimetllylolethane and trimethylolpropane.
The carboxylic acids that may be used
include, for example, acetic acid, propionic acid,
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butyric acid, pentanoic acid, hexanoic acid, heptanoic
acid, octanoic acid, nonanoic acid, decanoic acid,
undecanoic acid and the like, terephthalic acid,
and fatty acids such as stearic acid, oleic acid,
and tall oil acids and unsaturated acids such as
acrylic, methacrylic and crotonic acids.
The amines to which the present invention is
applicable are organic compounds which contain both
amino and hydroxyl groups including, for example,
monoethanolamine, N-methylmonoethanolamine, N-ethyl-
monoethanolamine, N-(n-propyl) monoethanolamine,
N-(isopropyl) monoethanolamine, N-(n-butyl) mono-
ethanolamine, diethanolamine, N,N-dimethylethanol-
amine, N,N-diethylethanolamine, N,N-di(n-propyl) ethanol-
amine, N,N-di(isopropyl) ethanolamine, N,N-di(n-butyl)-
ethanolamine and triethanolamine. Also useful can be
propanolamines such as monopropanolamine, dipropanol-
amine, and tripanolamine, as well as the aminophenols
such as p-aminophenol, m-aminophenol, and o-aminophenol.
The epoxides which are applicable in accordance
: with the invention can be any epoxide havin~ from two
to about thirty carbon atoms. Exemplary epoxides
include alkylene oxides such as ethylene oxide;
: propylene oxide-1,2; butylene oxide-1,2 and -2,3
~'73~)~5 12,337
pentylene oxide-1,2; hexylene oxide -1,2; octylene
oxide -1,2i and decylene oxide -1,2i and mixtures
of the same; epoxidized fatty alcohols derived from fatty
oils such as epoxidized soybean fatty alcohols
and epoxidized linseed oil fatty alcohols; cycloalkylene
epoxides including, for example, cyclohexane oxide,
cyclopentene oxide, cycloheptene oxidei aromatic epoxides
such as styrene oxide and 2-methyl styrene oxide; and
hydroxy-and halogen-substituted epoxides such as glycidol,
epichlorohydrin and epibromhydrin.
In accordance with the process of the invention, the
reaction of an epoxide with an active hydrogen containing
compound is catalyzed by the presence of a basic salt
of alkaline earth metal selected from the ~roup
consisting of calcium, strontium, barium and
mixtures of the same which are soluble in the
reactants and the reaction products produced thereby.
These basic alkaline earth metal salts may be
calcium, strontium, and barium alkoxides, amides
phenoxides, and the mutual reaction products of an
alkaline earth metal hexammoniate, an olefin oxide
and an organic nitride such as disclosed in U. S~
Patent 2,969,402 to Hill et al. Also suitable are
calcium, strontium, and barium compounds, such as
the salts thereof whichare convertable to soluble
basic salts, in situ, during the alkoxylation reaction.
Exemplary of such salts include calcium chloride, calcium
sulfate, calcium cyanide, barium bromide and the like.
3~
12,337
Basic salts of alkaline earth metals that are
suitable for use in accordance with the invention and
their method of preparation are known. However, a
preferred soluble basic salt of alkaline earth metal for
use as a catalyst in the invention, particularly in the
reaction of an epoxide and various monohydric alcohol
and polyol reactive hydrogen compounds is disclosed in
copending Canadian application Serial No. 359,573. In
copending Canadian application Serial No. 359,116 there
is disclosed a method of preparing various calcium,
strontium and barium alkoxides, the alcohol moiety
thereof being the same or similar to the alcohol or
polyol reactive hydrogen compound reactant co~ponent
which has been found to be a particularly efficacious
catalyst in various embodiments of the present invention.
Such metal alkoxides are, in general, prepared
by a two step process. In the first step of the process,
for example, calcium, strontium and bariu~ containing
raw materials such as calcium, strontium, and barium
metal, or hydrides or acetylides may be reacted with a
lower aliphatic alcohol having 1 to about 7 carbon atoms.
The concentration of metal in the lower alcohol may vary
from 0.01 to 20 percent. In the second step, the lower
alcohol metal alkoxide reaction product is reacted with
a polyol or "higher" alcohol having at least 4 and
preferably from 8 to about 30 or more carbon atoms, which
is the same or similar to the reactive hydrogen compound
to be reacted with the epoxide, thereby preparing a metal
alkoxide of the reacti~e hydrogen compound which is a
soluble basic salt having catalytic
10 .
B
6~5
12,337
activity. The lower alcohol introduced with the lower
metal alkoxide is removed from the final metal alkoxide
reaction product by any separation means that retains
the catalytic activity of the alkaline earth metal
alkoxide, with distillation being generally preferred.
Alternatively, the alkaline earth metal alkoxide of
a lower alcohol prepared in the first step may be added to a
reaction mixture comprising a reactive hydrogen compound and
epoxide wherein the reactive hydrogen compound is a polyol
or higher monohydric alcohol having at least 4 and preferably
from ~ to about 30 or more carbon atoms and the soluble basic
salt of the alkaline earth metal formed in situ has the
catalytic activity desired.
The amount of catalyst used in accordance
with the invention is not narrowly critical and
a catalytic effect has been noted with only a s~
amount thereof being present. In general, the
catalyst concentration can vary from 0.001 percent
to 10 percent by weight of calciu~, strontium, and barium
based on the wight of active hydrogen compound.
Concentrations of alkaline earth metal within the
range from about O.OS percent to about S.0 percent
by weight of active hydrogen compound are usually
preferred. The reaction rate, however, is dependent
on both temperature and catalyst concentratîon and to
achieve a given rate, more catalyst is required at a
low temperature than at a high temperature.
The invention will become more clear when
considered together with the following examples which
are set forth as being merely illustrative of the
~'7~ 5
12,337
invention and which are not intended, in any manner,
to be limitative thereof Uhless otherwise indicated,
all parts and percentages are by weight.
} LE 1
A mixture of 25 grams (0.19 moles) of calcium
ethoxide (prepared by the reaction of calcium metal
and ethanol) and 1000 grams (4.7 moles) of a mixture of
C12 to Cls primary alcohols (60% branched, 40% normal
iQomers) available under the tradename LIAL-125 from
Liquichemica Italia was heated at 90C under high vacuum
in a stirred flask distilling off the ethanol and then
transferred to a steel, 2.5-gallon autoclave equipped
with a stirrer, an automatic temperature controller,
and an automatic feéd controller. The autoclave was
heated to 110C, pressurized to 20 psig with nitrogen
and then to 60 psig with ethylene oxide. By automatic
control, 1685 grams (38.3 moles) of ethylene oxide was
fed to the autoclave at 110C over a period of 2 1/2
hours. After cookout to 33 psig, the product (2717
grams) was cooled, drained from the reactor, and
neutralized to a pH of 7 with acetic acid in a stirred
flask.
In a second run, 8.2 grams (0.15 moles~ of
potassium hydroxide in 1000 grams of the mixture of-
C12 to C15 primary alcohols hereinabove described was
charged into the 2.5-gallon autoclave and heated to
110C under 60 psig pres~ure as in run 1. 1685 grams
(38.3 moles) of ethylene oxide was then fed to the auto-
clave and reacted with the alcohol at 110C over a period
of 0.65 hours. After cookout, the product (2707 grams)
was cooled, drained from the reactor and neutrslized to
a pH of 7 with acetic acid.
~ ~ 5 ~3 ~1~ rj 12, 337
Gel permeation chromatography, a standard tech-
nique for determining the molecular weight distribution
of polymers and surfactants was used to evaluate the re-
action products. A comparison of the widths of gel per-
meation peaks at their half-heights, all run at constant
conditions, is a measure of the relative broadness of the
molecular weight distribution of the polymers or surfactants.
When the performance of the instrument is calibrated with
standards of known molecular weights, it is possible to
define the molecular weight range represented by the peak
width at half height.
Gel permeation chromatography results on the pro-
ducts of run #l and #2 hereof are reported in Table I, below:
TABLE I
~EL PER~EATION CHROMATOGRAPHY RESULTS
Peak Width At Molecular Weight Range
Catalyst One-~alf Hei~ht (cc) At One-Half Height
Basic Calcium
Alkoxide (Run #1) 2.9 360-820
Potassium
Hydroxide (Run #2) 4.4 320-1000
The catalytic effect using the basic calcium alkoxide
and potassium hydroxide is apparent from the above results.
Although the catalytic activity of the basic calcium alkoxide
is less than that of potassium hydroxide, the .~ore favorable
molecular distribution of the reaction products obtained with
this catalyst as compared to potassium hydroxide is apparent.
EXAMPLE 2
A mixture of a modified calcium amide containing
5.75 grams of calciu~ (0.14 moles) prepared according to the
method disclosed in U.S. Patent 2,969,402 to Hill et aL and
1000 grams (4.7 moles) of the mixture of C12 to C15 primary
alcohols of Example 1 was charged to the autoclave of
~ 3~j~ 12,337
Example 1 and 1687 grams (38.3 moles) of ethylene oxide
was reacted with it using the procedure of Example 1 at
110C and 60 psig over a period of 1.8 hours. After cookout,
the product (2673 grams) was cooled, drained from the re-
actor, and neutralized to a pH of 7 with acetic acid. The
calcium containing basic catalyst was soluble in the reaction
mixture drained from the reactor but precipitated therefrom
when neutralized with acetic acid. Gel permeation chroma-
tography results on the product for~ed are reported in Table
2, below:
Using the procedure and autoclave hereinabove
described, a mixture of 6.21 grams (0.16 moles) of sodium
hydroxide in 1000 gral~s (4.7 moles) of the mixture of
C12 to C15 primary alcohols of Example 1 was reacted with
1685 grams (38.3 moles) of ethylene oxide at 110C and 60
psig over a period of .75 hours. After cookout, the product
(2721 grams) was cooled and neutralized with acetic acid.
The sodium hydroxide catalyst was soluble in the reaction
mixture and did not precipitate when neutralized with ace-
tic acid. Gel permeation chromatography results on the
product formed are reported in Table 2, below:
TABLE 2
GEL PERMEATION CHP~OMATOGRAPHY RESULTS
Peak Width At Molecular Weight Range
Catalyst One-Half Height (cc) At One-Half Height
Modified Basic Calcium
Amide 2.9 360-840
Sodium Hydroxide 4.2 340-1050
The catalytic effect using the .~odified basic cal-
cium amide and sodium hydroxide materials is apparent, though
the catalytic activity of the basic calcium salt is somewhat
less than that of sodium hydroxide. However, the more favorable
~7~ 12,337
molecular distribution of the reaction products obtained
with the basic calcium salt material as compared to sodium
hydroxide is apparent from the above results.
EXAMPLE 3
Run #1: A mixture of calcium ethoxide (0.072
moles) in ethanol (140cc) prepared by the reaction of
calcium metal and ethanol was added to 500 grams (2.7
moles) of l-dodecanol and heated in a stirred flask at
110C under high vacuum to remove the ethanol. The re-
sulting mixture was charged to the autoclave of Example 1
wherè 770 grams (17.5 moles) of ethylene oxide were
added, and, using the procedure of Example 1, reacted
at 140C and 60 psig. After completion of the reaction,
a portion of the product (507 grams) was removed from
the autoclave and neutralized with acetic acid. The cal-
cium containing basic catalyst was soluble in the reaction
mixture removed from the autoclave until neutralized with
acetic acid. Gel permeation chromatography results for
the reaction product are reported in Table III, below.
To the remaining portion of the reaction product
in the autoclave was added 767 grams (13.7 moles) of
propylene oxide at 140C and 60 psig. A portion of the
resulting product (525 grams) was removed from the auto-
clave and neutralized. The molecular weight of the pro-
duct was determined to be 832.
Run #2: Using the autoclave and procedure herein-
above described, a mixture of potassium hydroxide (0.072
moles) and 500 grams ~2.7 moles~ of l-dodecanol was stripped
in a stirred flask at 110C and high vacuum and then charged
to the autoclave. Ethylene oxide (757 grams - 17.2 moles)
15.
~ 12,337
was reacted with the charge in the autoclave at 140C
and 60 psig. After completion of the reaction, a portion
of the product (559 grams) was removed from the autoclave
and neutralized with acetic acid. The gel permeation
chromatography results are reported in Table III, below.
To the remaining portion of the reaction mixture
in the autoclave were added 701 grams (12.5 moles~ of
propylene oxide at 14QC and 60 psig. After completion
of the reaction, a portion of the product (555 grams) was
removed from the autoclave and neutralized. The molecular
weight of the product was determined to be 926.
TABLE III
GEL PERMEATION CHROMATOGRAPHY RESULTS
~olecular
Peak Width At Weight Range
Catalystne-Half Hei~ht (cc) One Half Hei~ht
Run #1 Calcium Salt 2.9 290-640
Run #2 Potassium Hydroxide 4.5 270-930
The catalytic effect using the basic calcium salt
and potassium hydroxide in the reaction with both ethylene
oxide and propylene oxide is apparent. While the catalytic
activity of the basic calcium salt was found to be lower
than that of potassium hydroxide, the narrower m~lecular
weight distribution of the reaction products as compared
to potassium hydroxide was very favorable.
EXAMPLE 4
.
The autoclave and procedure of Example 1 were
employed in this Example during the following reactions.
, .
16.
~r~ 12~337
Run #1: Calcium ethoxide (0.5 moles) in 767
grams of ethanol was added to 853 grams (11.5 moles) of
butanol and the ethanol was removed by distillation yield-
ing a butanol solution containing 0.~4 les of calcium
per 1000 grams of solution.
A quantity of butanol (795 grams - 10. 7 mole8)
was mixed with 250 grams of the butanol solution containing
calcium prepared above and charged to the autoclave.
Propylene oxide t3710 ml. - 66 moles) was addet to the
autoclave at 115C under 60 psig at a rate that maintained
a constant pressure in the autoclave. After completion of
the reaction, the product (3063 grams) was neutralized with
phosphoric acid. The molecular weight and molecular weight
range results are reported in Table IV, below.
Run #2: Using the procedure of Run #l hereof, a
50/50 weight percent mixture of ethylene oxide and pro-
pylene oxide was reacted with butanol. The molecular
weight and molecular weight range results are reported
in Table IV.
Run #3 Using the procedure of Run #l hereof, a
75/25 weight percent mixture of ethylene oxide and propylene
oxide was reacted with butanol and the results are reported
in Table IV.
Runs #3, 4, and 5 were run using the alkylene oxide
and butanol reactants of Runs #1, $2 ~nd #3 hereof respec-
tively except that in each of these runs, preformed
potassium butylate was employed as the catalyst. Results
determined for the products produced in Runs 4, 5, and 6 are
reported in Table IV. The catalyst compositions employed
in test runs 1, 2, and 3 were soluble in the reaction mix-
tures prior to neutralization.
12,337
~'36~
The catalytic effect using the soluble basic
calcium alkoxide and potassium butylate materials is
apparent. It is also shown that products having a sig-
nificantly narrower molecular weight distri~bution are
obtained with the basic calcium salt catalyst as com-
pared with the potassium butylate catalyst.
: 18.
12, 337
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12,337
EXAMPLE 5
A 100 cc "rocking" autoclave reactor equipped
with automatic temperature control means i8 used in this
Example. In each test run of this Example, 15.0 grams
(0.075 moles) of lauric acid containing 0.14 moles of
the catalyst noted below per mole of lauric acid and 33.0
grams (0.75 moles) of ethylene oxide are charged into the
reactor, the reactor i8 closed and then heated at 110C
and autogenous pressure for 20 hours. Upon completion of
the reaction, unreacted ethylene oxide is stripped from
the reaction mixture and collected in a dry ice trap.
The catalyst is prepared by reacting an appropriate
amount of calcium, strontium, or barium metal with ethanol
at reflux in a flask protected from atmospheric moisture
and then mixing 20 grams of the metal ethoxide solution
with sufficient lauric acid to form a solution containing
0.14 moles of the appropriate metal per mole of lauric
acid; after removal of the ethanol. The ethanol is
removed from the lauric acid solution by distillation at
100C and 2 mm vacuum.
Run #1: In this run, calcium ethoxide is prepared
using 0.23 moles of calcium metal per 1000 grams of ethanol
and then 32 grams of lauric acid is mixed with 20 grams of
the calcium ethoxide to give a solution of 0.14 moles of
calcium per mole of lauric acid.
Run #2: 20 grams of strontium ethoxide prepared
in the proportion of 0.36 moles per 1000 grams of ethanol
is mixed with 50.2 grams of lauric acid to give a ~olution
containing 0.14 moles of strontium per mole of lauric acid.
20.
~ 12,337
Run #3: Barium ethoxide i8 prepared using 0.38
moles of barium metal per 1000 grams of eth~nol and then
52.8 grams of lauric acid is ~ixed with 20 gram~ of the
barium ethoxide to give a solution containing 0.14 moles
of barium per mole of lauric acid.
In each of the runs, substantially all of the
ethylene oxide iB reacted with lauric acid to give a
reaction product that i8 a mixture of poly(oxyethylene)
laurate, poly(oxyethylene) dilaurate, and poly(oxyethylene).
EXAMPLE 6
A mixture of 1.5 liters of calcium ethoxide in
ethanol (prepared by reacting 28 grams (0.70 moles) of
calcium metal with 1.5 liters of ethanol at reflux) and
600 grams (6.5 moles) of glycerine is heated under
vacuum to remove the ethanol.
Five hundred and sixty five grams (6.14 moles
of glycerine) of the solution containing glycerine and
basic salt of calcium is charged into a 2 gallon steel
autoclave reactor equipped with an automatic temperature
controller, an automatic pressure and reactant feed con-
troller, and circulating means for the reactants. The
autoclave is heated to 117C, pressurized to 12 psig with
nitrogen and tllen to 70 psig with propylene oxide. Over
a 2 hour period, 365 grams (6.3 moles) of propylene oxide
is fed to the autoclave while maintaining the temperature
at 117C. The temperature of the autoclave i8 then raised
to 135C and an additional 3390 grams (58.4 moles) of
propylene oxide is added over a period of 5 hours while
maintaining the temperature at 135C and a constant pressure.
After all the propylene oxide is added, the autoclave is
21.
~r 1 ~
12 ~ 337
helt at 135C for one additional hour to ~chieve complete
reaction after which the reactor i8 cooled and the reaction
mixture is discharged and analyzed.
The reaction product i8 a clear ~olution which i8
determined to have a hydroxyl number of 238 from which a
molecular weight of 707 is calculated assuming a func-
tionality of 3.
EXAMPLE 7
A mixture of 123 grams of calcium ethoxide in
ethanol (prepared by reacting calcium metal with ethanol
at reflux) and 510 grams (5.5 moles) of phenol are heated
to 55C under 5 mm vacuum to distill off the ethanol. The
resulting solution contains 0.14 moles of calcium per 100
grams of phenol (0.6 weight percent calcium).
Five hundred and twenty grams of the phenol
solution prepared above (contains 5.5 moles phenol) is
- charged to the autoclave reactor of Example 1 which is
heated to 140C and pressurized to 60 psig using the pro-
cedure of Example 1. Over a period of 0.18 hours, 242
grams (5.5 moles) of ethylene oxide i8 fed to the auto-
clave. After cookout to a constant pressure (about 1 hour)
the reaction mixture is cooled and a sample of 114 grams is
drained from the reactor, neutralized with phosphoric acid
and analyzed for molecular weight. Before neutralization
the reaction product i8 a clear solution.
The 648 grams of reaction mixture (4.6 moles) re-
maining in the autoclave are reheated to 140C and brought
to a pressure of 60 psig with ethylene oxide. Over a period
of 0.3 hours, 208 grams (4.7 moles) of ethylene oxide are
fed to the reactor. After cookout to a constant pressure
' '
12,337
(about 40 minutes) the reaction mixture is cooled and a
sample of 119 grams of reaction product is drained from the
reactor, neutralized with phosphoric acid and analyzed for
molecular weight. The reaction mixture is a clear solution
before neutralization.
The reaction mixture remaining in the autoclave
(737 grams - 4.2 moles) is reheated to 140C and brought
to a pressure of 60 psig with ethylene oxide. Over a period
of 0.23 hours, 177 grams (4.0 moles) of ethylene oxide is
fed to the autoclave. After cookout to a constant pressure
(about 1 hour), the reaction mixture is cooled and drained
from the reactor, neutralized with phosphoric acid and
analyzed. The reaction product is a clear solution before
neutralization.
The reaction product samples taken during the three
steps of the process are determined to have the following
molecular weights:
First Step: molecular weight of 142
Second Step: molecular weight of 177
Final Step: molecular weight of 219
EXAMPLE 8
In a ~eries of test runs, l-dodecanol was
reacted with ethylene oxide in the autoclave reactor of
Example 1 using the procedure of Example l to evaluate
the catalysts noted ln Table II, below. In each run,
500 grams (2.7 moles) of l-dodecanol c~ntaining 0.10 to
0.12 moIes per liter of catalyst was charget to the auto-
clave reactor and reacted with approximately 6.7 moles
of ethylene oxide at 140~,except as noted,and 60 psig.
~ a ~!3~ 12,337
The products were neutralized with phosphosic acid,
filter, and analyzed. The analytical results are seported
in Table II and Table III, below.
The catalysts used were prepared as follows:
For the potassium catalyst, potassium hydroxlde was added
to l^dodecanol, and then water was removed at 110C and
lOmm vacuum. For the calcium, strontium, and barium
catalysts, the metal was first reacted under reflux with
excess ethanol or methanol to make a 0.5 mole per lieer
solution. The alkoxide solution in lower alcohol (ethanol
or methanol) was added to l-dodecanol and the lower alcohol
and any water present was removed at 110C and lOmm vacuum.
24.
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12, 337
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T~BLE III
GEL PERMEATION CHROMATOGRAPHY RESULTS
Molecular
Concentration ~eak Witth AtWeight Range At
Cataly~t (Wei~ht Percent) One-Half Hei~ht (cc~ e-Hslf Height
Potassium 0.48 4.5 270-930
hytroxide
Calcium 0.48 2.9 290-640
cthoxide I
Strontium O.97 3.1 290-690
ethoxide
Barium 1.~1 3.3 280-690
ethoxide
Calcium 0.48 3.3 280-690
methoxide
The results show that soluble basic salts of barium,
strontium, and calc$um catalyze the oxyethylat$on of the mono-
hydric alcohol to g~ve reaction products having a narrower
molecular weight distribution and lower pour points compared
~to protucts made with potassium hydroxide.
26.
