Hydroxyl compounds are oxyalkylated by contacting them with an alkylene oxide, such as ethylene oxide or propylene oxide, in the presence of a perfluorocarbon polymer containing pendant sulfonic acid groups.

FIELD OF THE INVENTION 
This invention relates to a process for oxyalkylation of compounds 
containing at least one hydroxyl group. More particularly, this invention 
relates to carrying out said oxyalkylation in the presence of a 
perfluorocarbon polymer containing pendant sulfonic acid groups. 
BACKGROUND OF THE INVENTION 
The reaction of alkylene oxides, such as ethylene oxide, with alcohols to 
yield an oxyalkylated alcohol has been known for many years. Commercially, 
liquid and gaseous sulfonic acids and sulfuric acids have been used as 
catalysts. The reactors necessary for containing such catalysts are very 
expensive and in addition, separation of the catalyst from the 
oxyalkylated product is difficult. 
Presumably, sulfonated polymeric substances, such as sulfonated 
styrene-divinylbenzene polymers or the Amberlyst series of sulfonated 
polymers (U.S. Pat. No. 3,037,052) would provide a source of sulfonic acid 
catalytic material that would avoid the problems of the conventional 
catalysts. However, these catalytic materials have not found wide 
acceptance in the art because of a number of defects associated with them. 
For example, residues from incomplete polymerization, along with initiators 
for the polymerization, leach out of sulfonated styrene-divinylbenzene 
resins under any but the mildest reaction conditions. In addition, the 
sulfonated copolymers in general are fragile, easily crumbled, materials 
which must be delicately handled. This is a definite drawback when 
commercial scale operations are involved. A further disadvantage is that 
the polymers have a low specific activity, so that a relatively large 
amount of the catalyst must be used. 
A final, but very significant, disadvantage of these catalysts is that they 
cannot be easily regenerated or reused, if the contaminants are not 
readily removed with warm hydrochloric acid (6N) or its equivalent. Any 
more-drastic treatment usually degrades the catalyst. 
SUMMARY OF THE INVENTION 
It has now been found that compounds containing at least one hydroxylic 
group can be oxyalkylated efficiently and economically with a flexible, 
easily fabricated catalyst having a high specific activity. This catalyst 
can be easily regenerated for example, by boiling in concentrated nitric 
acid, and its use leads to the formation of insignificant amounts of 
polymeric tars during the course of the reaction. The oxyalkylation 
reaction according to this invention comprises contacting the hydroxylic 
compound with an alkylene oxide in the presence of a perfluorocarbon 
polymer containing pendant sulfonic acid groups. 
DETAILED DESCRIPTION OF THE INVENTION 
A. The Reactants 
The hydroxylic compounds that can be oxyalkylated by the process of this 
invention include any organic compounds containing one or more hydroxy 
(--OH) groups. Water is also included within the scope of the term 
hydroxylic compound. Certain of the hydroxylic compounds contemplated for 
use within the scope of this invention may also be described by the 
formulas 
##STR1## 
wherein R is hydrogen or hydrocarbyl, R' is hydrocarbyl, hydrocarbyl 
--X'--, or hydrogen, X' is oxygn or sulfur, x is an integer, preferably of 
1 to 6, with the proviso that when R is hydrogen, x is one, z is an 
integer from 1 to 3, and y is 3-z. Of particular interest are those 
hydroxylic compounds wherein R is hydrogen, alkyl of 1-20 carbon atoms, 
phenyl, alkylphenyl of 7 to 30 carbon atoms, hydroxyalkyl of 2 to 20 
carbons, or hydrocarbyloxyalkyl of the formula hydrocarbyl 
--O-alkyl].sub.g where the hydrocarbyl group contains 1-20 carbon atoms, 
alkyl is ethylene or propylene and g is at least one. 
The hydrocarbyl portion of the hydroxylic compound may be aliphatic, 
cycloaliphatic, aromatic, or a combination of two or more types of 
hydrocarbon groups. The hydrocarbyl radical may contain any substituents 
that do not react with the alkylene oxide under the reaction conditions of 
the instant invention more readily than does a hydroxyl group. The 
substituents on the hydrocarbyl group also should not be of a type that 
might poison the catalyst. Substituent groups that should be avoided can 
be readily determined by one skilled in the art. Typical of such groups 
are amino, mercapto, and metal carboxylate. Substituent groups that may be 
present on the hydrocarbyl portion of the hydroxylic compound without 
affecting the oxyalkylation reaction include nitro, hydrocarbyloxy, halo, 
phosphonate, phosphate, 
##STR2## 
The R group is preferably a straight or branched-chain alkyl of 1 to 20 
carbon atoms, H or phenyl. 
Particularly preferred hydroxylic compounds are water, methanol, ethanol, 
1-dodecanol, 1-butanol, isobutanol, ethylene glycol, glycerol, 
pentaerythritol, sorbitol, phenol, and alkylated phenols. 
The alkylene oxides intended for use within the scope of this invention 
fall within the general formula 
##STR3## 
wherein each of R.sup.1 and R.sup.2 is hydrocarbyl of 1 to 20 carbon atoms 
or R.sup.1 and R.sup.2 together with the two carbon atoms form a five- or 
six-membered cycloaliphatic ring. 
Typical alkylene oxides contemplated for use within the scope of this 
invention are ethylene oxide, propylene oxide, 1,2-butylene oxide, 
2,3-butylene oxide, 1,2-pentylene oxide, 2,3-pentylene oxide, 1,2-hexylene 
oxide, 3-methyl-1,2-pentylene oxide, 2,3-octyleneoxide, 
4-methyl-2,3-octylene oxide, 4-methyl-1,2-hexylene oxide, and 
3-methyl-1,2-butylene oxide. Because of their commercial availability, 
ethylene oxide and propylene oxide are preferred. Ethylene oxide is 
particularly preferred. 
B. The Catalyst 
The catalyst used for the oxyalkylation reaction of this invention is a 
perfluorocarbon polymer containing pendant sulfonic acid groups. A 
preferred catalyst is the perfluorocarbon polymer having the repeating 
structure 
##STR4## 
wherein n is 0, 1 or 2, R.sup.3 is --F or perfluoroalkyl of 1 to 10 carbon 
atoms, Z is --O--CF.sub.2 --CF.sub.2).sub.m, --OCF.sub.2 CFY-- or 
--OCFYCF.sub.2 -- where m is an integer from 1 to 9, and Y is --F or 
trifluoromethyl. 
Useful perfluorocarbon polymers and their preparation are described in U.S. 
Pat. Nos. 3,041,317, 3,282,875, 3,624,053 and 3,882,093, the disclosures 
of which are hereby incorporated by reference. 
Catalysts of the above-noted structure typically have a molecular weight of 
between 1,000 and 500,000 daltons. 
Polymer catalysts of the above-noted structure can be prepared in various 
ways. One method, disclosed in Connolly et al, U.S. Pat. No. 3,282,875, 
and Cavanaugh et al, U.S. Pat. No. 3,882,093, comprises polymerizing vinyl 
ethers of the formula: 
##STR5## 
in a perfluorocarbon solvent using a perfluorinated-free radical 
initiator. Since the vinyl ethers are liquid at reaction conditions, it is 
further possible to polymerize and copolymerize the vinyl ethers in bulk 
without the use of a solvent. Polymerization temperatures vary from 
-50.degree. to +200.degree. C. depending on the initiator used. This 
special method of operation is claimed in copending application, Ser. No. 
306,482, filed Sept. 28, 1981 now U.S. Pat. No. 4,409,403. Pressure is not 
critical and is generally employed to control the ratio of the gaseous 
comonomer to the fluorocarbon vinyl ether. Suitable fluorocarbon solvents 
are known in the art and are generally perfluoroalkanes or 
perfluorocycloalkanes, such as perfluoroheptane or 
perfluorodimethylcyclobutane. Similarly, perfluorinated initiators are 
known in the art and include perfluoroperoxides and nitrogen fluorides. It 
is also possible to polymerize the vinyl ethers of the above structures in 
an aqueous medium using a peroxide or a redox initiator. The 
polymerization methods employed correspond to those established in the art 
for the polymerization of tetrafluoroethylene in aqueous media. 
It is also possible to prepare catalysts for the present invention by 
copolymerizing the vinyl ethers of the above structure with 
tetrafluoroethylene and/or perfluoroalphaolefins. A preferred copolymer 
prepared by polymerizing perfluoroethylene with a perfluorovinyl ether 
containing sulfonic acid groups would have the following structure: 
##STR6## 
wherein n is 1 or 2 and the ratio of x' over y' varies from about 2 to 50. 
Polymers of this structure are available commercially under the tradename 
of NAFION resin (E. I. duPont). Catalysts of this structure offer the 
advantages of high concentrations of accessible acid groups in a solid 
phase. As indicated by the x'/y' ratio above, the equivalent weight 
(expressed as grams polymer per sulfonic acid group) can range from 644 or 
810 upwards depending on whether n=2 or 1. 
W. G. F. Grot et al. in "Perfluorinated Ion Exchange Membranes", a paper 
presented at the May 1972 National Meeting of the Electrochemical Society, 
plots water absorption for the perfluorinated ether polymer sulfonic acid 
against equivalent weights over the range 800 to 2000; as indicated 
thereby the more active polymers have equivalent weights somewhat below 
2000. Generally preferred are equivalent weights of 900 to 1700 and more 
preferably below 1500. The equivalent weight of the catalyst used in the 
Examples was 1200. 
The catalyst may be used in the process of this invention in a variety of 
physical forms, that is, it may be fabricated into sheets, hollow tubes, 
granules having a particle size of from 6 mesh to less than 400 mesh, 
fibers, and the like. The catalyst may be used alone or it may be 
supported, for example, by coating it onto a metal or combining with other 
common catalyst supports as is well known in the art. The catalyst is 
insoluble in and inert to deactivation by the reaction mixtures and 
conditions used in the process of this invention. For this reason, the 
catalyst is easy to separate from the reactants and products. Furthermore, 
the life of the catalyst is considerably longer than is the life of 
conventional sulfonated resin catalysts. 
In order for the resins of this invention to have catalytic activity of a 
degree sufficient to make them useful for the process of this invention, 
it is necessary that they be activated by (1) contacting the resin with a 
strong acid having a pKa less than zero at elevated temperature, for 
example, contacting with 70% nitric acid at 110.degree. C., and (2) 
washing the resin with water until the wash water is neutral. When water 
is not the reactant being oxyalkylated, it is necessary to either dry the 
catalyst to constant weight to remove the water or to displace the water 
with the hydroxylic reactant to be used prior to the introduction of the 
alkylene oxide. 
The catalyst may be cleaned after use using the same procedure described 
above. The cleaning process can be used to remove any residual tars that 
form during the reaction, to restore any lost degree of catalytic 
activity, or to remove residual hydroxylic reactants when the catalyst is 
to be used with a different reactant. 
C. The Reaction Conditions 
The hydroxylic compound to be oxyalkylated using the process of this 
invention is contacted with an alkylene oxide in the presence of a 
perfluorocarbon polymer having pendant sulfonic acid groups. The 
temperature and pressure of the reaction zone are maintained so as to 
maximize the production of the desired products. Usually, the product of 
choice is the one having only one oxyalkyl group per hydroxylic group in 
the hydroxylic compound; however, in certain situations it will be 
desirable to form a polyoxyalkylene group on the hydroxylic compound. The 
molar ratios of reactants necessary to achieve the desired product will be 
readily apparent to one skilled in the art and will vary with the product 
desired. Thus, for example, the mol ratios for water and ethylene oxide 
generally used heretofore are from about 1:1 up to 50:1 or more; commonly 
used are mol ratios of 5:1 or 10:1 to 30:1 (i.e., weight ratios of about 
2:1 or 4:1 to 12:1). Thus, a generally preferred range for initial weight 
ratios can be from 3:1 to 15:1. 
Pressure and temperature are likewise adjusted to achieve the desired 
product. Again, determination of the desirable ranges for each set of 
reactants is well within the skill of the art. Usually the temperature is 
maintained between 0.degree. C. and 150.degree. C. Generally, the 
temperature initially is at least 50.degree. C. (note the examples 
following) and with the preferred procedure at reflux (i.e., 100.degree. 
C. when using water). Thus, a generally preferred temperature range is 
50.degree. to about 100.degree. C. or up to somewhat higher such as 
110.degree. or 125.degree. C. The reactions contemplated for use in the 
process of this invention ordinarily are most readily carried out at 
atmospheric pressure. However, higher or lower pressures may be employed 
if desired. 
When a mono-oxyalkylated hydroxylic compound is desired, it can be prepared 
with up to 99 percent or greater selectivity using a preferred method of 
operation provided as part of this invention. This preferred method is not 
limited to the use of perfluorocarbon polymers having pendant sulfonic 
acid groups. It is equally applicable for use with any insoluble solid 
acidic catalyst, that is, one which is not soluble or only soluble to a 
negligible extent in the reactants or products under the process 
conditions described herein. However, the perfluorocarbon polymers are 
preferred because of their above-described advantages as oxyalkylation 
catalysts. 
The operation of this preferred steady-state method can be described as 
follows. The hydroxylic compound is heated to vaporization in a reflux 
zone. This vaporized mixture then passes through the catalyst zone to a 
condensing zone where the vaporized mixture becomes liquid and returns to 
the catalyst zone where it contacts both vaporized hydroxylic compound and 
the solid acidic catalyst. The alkylene oxide is introduced into the 
reflux zone, the condensing zone, or the catalyst zone. It is necessary 
for the reaction conditions to be such that the alkylene oxide is present 
to some extent in the catalyst zone. 
When the hydroxylic compound and the alkylene oxide come into contact in 
the catalyst zone, a monoalkylated hydroxylic compound is formed. The 
monooxyalkylated derivative then returns (as a mixture with unreacted 
hydroxylic compound) to the reflux zone where it is recovered by 
fractionation of the mixture of hydroxylic compound and mono-oxyalkylated 
derivative thereof (the unreacted hydroxylic compound being sent overhead 
to the catalyst zone). 
A mono-oxyalkylated hydroxylic compound essentially free of 
polyoxyalkylated derivatives is continuously prepared by the above method. 
The process also minimizes the amount of energy needed to carry it out, 
because the heat of reaction generated by oxyalkylation is removed in the 
condensation zone which is preferably separate from the catalyst zone. 
Thus, heat of reaction is converted to heat of vaporization in the 
catalyst zone, thereby maintaining microscopic temperature control at the 
catalyst sites. Heat of reaction is removed in the condensation zone, 
allowing great flexibility in construction and ease of maintenance of the 
reactor being used. 
The preferred mode of operation is especially suitable in instances wherein 
the oxyalkylated derivative will further react with the alkylene oxide at 
a greater rate than the hydroxylic compound. The selectivity for the 
mono-oxyalkylated derivative may be improved by means of the process of 
the instant invention. In this method the oxyalkylated derivative must 
have a higher boiling point than the hydroxylic compound. Furthermore, the 
alkylene oxide preferably has a much lower boiling point, preferably at 
least 10.degree. C. lower, than either the hydroxylic compound or its 
oxyalkylated derivative so that it will not be returned in its unreacted 
form to the refluxing mixture. In general, any difference in boiling point 
of, for example, at least 5.degree. C. between the oxyalkylated derivative 
and the hydroxylic compound is suitable for carrying out this preferred 
process. Preferably, the oxyalkylated derivative will have a boiling point 
at least 10.degree. C. greater than the boiling point of the hydroxylic 
compound. 
Variations of the above process will be readily apparent to one skilled in 
the art. For example, the hydroxylic compound may be condensed in the same 
zone where the solid acid catalyst is present or it may be condensed at a 
point above the catalyst and fed by gravity into the catalyst zones. 
Apparatus used to carry out the above process may be of various designs. 
One such type is described below and designated as a reactor-fractionator. 
The following examples are presented for the purpose of illustrating the 
invention and should not in any way be construed as limiting the invention 
being claimed herein.

EXAMPLE 1 
Reaction of Ethylene Oxide With Ethanol in a Flowing Tube Reactor 
Nafion.RTM. fibers (0.006" diameter, 66 fibers, 50 inches long tied at the 
midpoint, 6.71 g catalyst weight) were fitted as a parallel bundle inside 
a polypropylene tube (3'.times.1/4" O.D..times.0.040" wall). The catalyst 
was prepared by heating with 70% nitric acid at 80.degree.-100.degree. C., 
then equilibrated with absolute ethanol under flow at 53.degree. C. before 
introduction of ethylene oxide at a tee prior to the inlet fittings (the 
tube was suspended in a forced-fan oven maintained by a thermistor 
temperature controller). Samples were collected in a graduated cylinder 
and analyzed by gas chromatography with 2-methoxyethanol as internal 
standard. The results are presented in Table I. 
TABLE I 
__________________________________________________________________________ 
Volume 
Ethylene 
in Oxide, 
Ethanol 
H.sub.3 CCH.sub.2 OCH.sub.2 CH.sub.2 OH 
H.sub.3 CCH.sub.2 O(CH.sub.2 CH.sub.2 
O).sub.2 H 
Sample 
ml ml/min 
ml/min 
% weight/volume 
% weight/volume 
__________________________________________________________________________ 
1 20 3-3.5 
0.56 0.6 -- 
2 10 3-3.5 
0.56 4.2 -- 
3 15 8 0.56 -- -- 
4 7 8 0.56 6.3 -- 
5 17 14 0.56 -- -- 
6 6 14 0.56 11.9 1.5 
7 17 25 0.56 -- -- 
8 11 22 0.56 17.5 3.3 
9 20 35-37 
0.56 -- -- 
10 10 34 0.56 23.8 5.3 
11 23 45 0.56 -- -- 
12 13 44 0.56 29.6 7.7 
13 22 58 0.56 -- -- 
14 12 57 0.56 30.1 9.6 
15 21 72-75 
0.56 -- -- 
16 8 72-75 
0.56 37.9 15.5 
17 26 35 0.28 -- -- 
18 5 35 0.28 30.2 12.3 
19 20 47 0.28 -- -- 
20 13 42-43 
0.28 29.6 1 (integrator off 
scale) 
21 18 85 0.28 -- -- 
22 10 85 0.28 20.5 8.8 
23 &lt;2 85 0.28 24.7 8.8 
__________________________________________________________________________ 
EXAMPLE 2 
Reaction of Ethylene Oxide With Methanol in a Flowing Tube Reactor 
The reactor of Example I was cycled in the usual manner and equilibrated 
with methanol under flow (0.50 ml/min at 40.degree. C.). Ethylene oxide 
was introduced at atmospheric pressure through a flowmeter to a tee at the 
entrance of the reactor. The temperature was raised to 51.degree. C. where 
reaction visibly proceeded readily. At higher flow rates of ethylene 
oxide, some gas was seen to escape from the outlet of the reactor 
indicating incomplete absorption/reaction. Portions of collected samples 
were mixed with an equal volume of 10% w/v 2-ethoxyethanol in ethanol for 
analysis by gas chromatography. The results are shown in Table II. 
TABLE II 
______________________________________ 
Ethyl- 
lene 
Sam- Oxide T CH.sub.3 OCH.sub.2 CH.sub.2 OH 
CH.sub.3 O(CH.sub.2 CH.sub.2 O).sub.2 H 
ple ml/min (.degree.C.) 
% weight/volume 
% weight/volume 
______________________________________ 
1 2.5 40 0 0 
2 2.5 51 2.1 trace 
3 6 51 4.5 trace 
4 12 51 8.3 trace 
5 25 51 15.3 1.3 
6 50 51 21.1 3.8 
______________________________________ 
EXAMPLE 3 
Reaction of Ethylene Oxide With Water in Integrated Reactor-Fractionator 
The bulbs of an eight-bulb Allihn condenser evacuated in the outer jacket 
were packed loosely with wads of wet Nafion fibers (9.8 g total, wet) 
which had been converted to the hydrogen form by treating at 
80.degree.-100.degree. C. with 70% nitric acid and washing with water 
until the wash water was neutral. This catalyst section was fitted atop a 
reflux-fractionator apparatus which consisted of (in ascending order): a 
500 ml r.b. flask with thermometer side arm, a 30.times.2 cm vigreaux 
column, insulated, and a short connecting tube with a side arm. A reflux 
condenser and bubbler were connected to the top of the catalyst section to 
observe any exit gas flow and to return reactants to the catalyst section. 
The flask was charged with 100 ml of water, 50 mg of NaHCO.sub.3, and a 
few boiling chips. Reflux was established through the catalyst section, 
then ethylene oxide was introduced through the side arm into the tube 
below the catalyst section. Flow was maintained at 30 ml/min for 18 hours, 
then increased to 60 ml/min for 2 hours, and then to 80 ml/min for 7.5 
hours. The ethylene oxide flow was terminated overnight while reflux was 
maintained. The ethylene oxide flow was resumed at 80 ml/min for an 
additional 8 hours; the reaction was terminated at a boiling temperature 
of 197.degree. C. (730 mm) of the flask contents. Most of the pot contents 
(340.0 g) were distilled through a 30.times.1 cm vigreaux column to yield 
the results shown in Table IIIA. 
TABLE IIIA 
__________________________________________________________________________ 
Product of Example 3A 
Fraction 
T.sub.head (.degree.C.) 
T.sub.pot (.degree.C.) 
wt (g) 
% Remarks 
__________________________________________________________________________ 
1 99-195.5 
193-202 
3.4 1.0 
2 195.5-201 
202-245 
230.0 
68.0 
HOCH.sub.2 CH.sub.2 OH 
3 201-242 
245-255 
7.6 2.2 
4 242-247.5 
255-275 
40.5 
12.0 
HOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH 
5 247.5-256 
275- 15.6 
4.6 
Residue 41.1 
2.1 
__________________________________________________________________________ 
The high oligomer (n&gt;1) content of the distillate in IIIA prompted a brief 
investigation of the effect of ethylene oxide flow rate and efficiency of 
the fractionating column. 
After removal of the pot contents of the reactor-fractionator from the 
experiment above, the catalyst section was washed by refluxing with fresh 
water in the pot for 1 hour; the pot contents were removed and replaced 
with 100 ml of fresh distilled water containing 50 mg of NaHCO.sub.3. 
Reflux was again established and ethylene oxide was introduced at a flow 
rate of 16 ml/min for 150 hours. The boiling temperature of the pot 
contents was then 183.degree. C. (730 mm Hg). A small sample was removed 
for analysis and the remainder of the pot contents (314.3 g) was distilled 
(730 mm Hg) through a 1.times.30 cm vigreaux column to yield the results 
shown in Table IIIB. 
TABLE IIIB 
__________________________________________________________________________ 
Fraction 
T.sub.head (.degree.C.) 
T.sub.pot (.degree.C.) 
wt (g) 
% Remarks 
__________________________________________________________________________ 
1 98-186 
156-195 
16.1 
5.1 
2 186-193 
195-197 
6.3 2.0 
3 193-200 
197-218 
254.5 
81.1 
HOCH.sub.2 CH.sub.2 OH 
4 200-241 
218-248 
13.4 
4.2 
5 241-253 
248-305 
16.3 
5.2 
HOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH 
6 253-266 
305-320 
2.1 0.7 
Residue 4.7 1.5 
__________________________________________________________________________ 
The catalyst section was again washed as above; the vigreaux column used in 
the reactor-fractionator was replaced by a 30.times.2 cm vacuum-jacketed 
fractionating column packed with stainless steel helices. Reflux was 
established using 50 ml of distilled water and 50 mg of NaHCO.sub.3 in the 
pot. Ethylene oxide was introduced at a flow rate of 10-14 ml/min. and 
continued until the pot contents had reached a boiling temperature of 
195.degree. C. (730 mm Hg). Gas chromatography of the neat pot contents 
(on a Carbowax 20M column) revealed only traces of diethylene glycol; the 
sole organic peak (&gt;99%) was ethylene glycol. 
Control (without catalyst) 
The reactor-fractionator above was charged with 100 ml of water, 50 mg 
NaHCO.sub.3 and boiling chips. The catalyst section was replaced by an 
identical Allihn condenser (evacuated outer jacket) without the 
Nafion.RTM. fiber catalyst. Reflux was established through this section, 
then ethylene oxide was introduced at 15 ml/min. Although little gas was 
observed escaping through the bubbler initially, rapid gas flow was 
established within an hour. Ethylene oxide flow was continued for 6 hours. 
The contents of the pot showed a weight loss of 2.1 g and only minute 
traces of organic materials, primarily ethylene glycol, on gas 
chromatography. 
EXAMPLE 4 
Reaction of Ethylene Oxide With Methanol in Integrated Reactor-Fractionator 
A bundle of parallel Nafion.RTM. fibers (0.006" diameter, 45 fibers 180 cm 
long, suspended from their midpoint, 4.48 g total weight) was fitted 
inside a straight tube condenser and the outer jacket was evacuated. The 
catalyst was prepared as described in Example 1 and the assembled 
reactor-fractionator (with the stainless-steel helice-packed fractionator) 
brought up to reflux with methanol to equilibriate the catalyst. The 
reactor was cooled and allowed to drain; the pot contents were replaced 
with 80.1 g of fresh methanol containing 50 mg of NaCHO.sub.3. After 
establishing reflux through the catalyst section, ethylene oxide was 
introduced at 100-200 ml/min. over a period of 8.24 hours. When the 
boiling temperature of the pot contents reached 126.5.degree. (730 mm Hg) 
the reaction was halted and the reactor allowed to drain down. A portion 
(202.1 g) of the pot contents (203.6 g) was distilled (730 mm Hg) through 
a 30.times.1 cm vacuum-jacketed vigreaux column to yield the results shown 
in Table IVA. 
TABLE IVA 
__________________________________________________________________________ 
net % of 
Fraction 
T.sub.head (.degree.C.) 
T.sub.pot (.degree.C.) 
wt (g) 
product 
Remarks 
__________________________________________________________________________ 
1 65-122 
124-125 
7.2 3.6 
2 122-124.5 
125-198 
173.5 
85.8 CH.sub.3 OCH.sub.2 CH.sub.2 OH 
3 124.5-191 
198-199 
0.8 0.4 
4 191-194 
199-262 
14.1 
7.0 CH.sub.3 O(CH.sub.2 CH.sub.2 O).sub.2 H 
Residue 5.4 2.5 
__________________________________________________________________________ 
A second preparation using an ethylene oxide flow of 15-20 ml/min. required 
a correspondingly longer time (46 hours) to complete the reaction; gas 
chromatographic analysis on a Carbowax 20M column showed the only organic 
product to be 2-methoxyethanol with a trace of methanol remaining. 
EXAMPLE 5 
Reaction of Ethylene Oxide With Ethanol in the Integrated 
Reactor-Fractionator 
The catalyst section and reactor-fractionator were prepared as in Example 4 
and equilibrated with ethanol under reflux. The pot contents were replaced 
with 70.4 g of fresh absolute ethanol and reflux was established through 
the catalyst section. Ethylene oxide was introduced at a flow rate of 
15-25 ml/min. for a period of 32 hours; the boiling temperature of the pot 
contents rose to 132.degree. C. (730 mm Hg). A small sample of the pot 
contents (133.5 g total) was removed for analysis; the remainder (132.1 g) 
was distilled (730 mm) through a 30.times.1 cm vacuum-jacketed vigreaux 
column to yield the results shown in Table V. 
TABLE V 
__________________________________________________________________________ 
net % of 
Fraction 
T.sub.head (.degree.C.) 
T.sub.pot (.degree.C.) 
wt (g) 
product 
Remarks 
__________________________________________________________________________ 
1 76.5-126 
117-135 
11.0 
8.3 
2 126-133 
135-136 
2.4 1.8 
3 133-136 
136-195 
108.1 
82.4 CH.sub.3 CH.sub.2 OCH.sub.2 CH.sub.2 OH 
4 136-189 
195-279 
5.5 4.2 
Pot Residue 1.0 2.8 
__________________________________________________________________________ 
In the foregoing examples, the mol ratio of the hydroxy compound to 
ethylene oxide ranged from about 2 to 100. Thus, for example, the mol 
ratios for samples 6, 12 and 16 in Table I were approximately 13:1, 4:1 
and 2:1, respectively; and for samples 4, 5 and 6 in Table II were 
approximately 23:1, 11:1 and 6:1, respectively. In Example 3 the mol ratio 
when starting with a nominal flow rate of 80 ml/min. for ethylene oxide 
was estimated at 25:1 at minimum refux conditions up to 50:1 for average 
reflux conditions, the mol ratio decreasing as the reaction with water 
nears completion. 
As illustrated, the present process using a sulfonated perfluorocarbon 
ether is decidedly superior to other processes, which are compared as 
follows: Reed et al in an article in Industrial and Engineering Chemistry, 
Vol. 48, pages 205-208 (February, 1956) proposed a process for hydrating 
ethylene oxide using certain acidic ion exchange resins. For example, the 
conversion rate at 108.degree. C. (226.degree. F.) in Example 12 (assuming 
a maximum of 1 gm. catalyst per milliliter of bed) was only about 0.00015 
moles ethylene oxide per minute per gram of catalyst (which is a measure 
of the turnover rate of ethylene oxode at the catalyst site, i.e., a 
measure of catalyst efficiency). For all of Reed et al's data, the best 
observed run is Run 10A which gives an efficiency of 0.00033 moles of 
ethylene oxide per minute per gram of catalyst. Also, Othmer et al in an 
article in Industrial and Engineering Chemistry, Vol. 50, pages 1235-1244 
(September, 1958) presents data on hydration of ethylene oxide using an 
Amberlite ion exchange resin as catalyst and Othmer et al's best result 
comparable to Example 1 hereinabove at about the same temperature 
(50.degree. C. versus 50.degree. C.), namely, Column 8 of Table V (on page 
1240 of Othmer et al), gave an efficiency of 0.000153 moles of glycol per 
minute per gram of resin. This compares to an obtainable efficiency of the 
present sulfonated fluorocarbon ether polymer of 0.00055 moles per minutes 
per gram of catalyst of monoethoxylated ethanol and diethoxylated ethanol 
in Sample 16 of Table I above. Othmer et al's results in Col. 1, Col. 2 
and Col. 7 of their Table V--all at 80.degree. C.--a much higher 
temperature at which greater efficiencies would be expected--, gave 
0.000217, 0.000095 and 0.000447 moles per minute per gram, all of which 
are lower than noted above with the sulfonated fluorocarbon ether polymer 
at the lower temperature of 53.degree. C. Japanese Pat. No. 38-4858 
describes the reaction of methanol and 2 moles of ethylene oxide at a 10:1 
molar ratio at 65.degree. C. with a styrene, strongly acidic cation 
exchange resin. At a reaction time of 60 minutes and a yield of 34.3%, the 
catalyst efficiency is 0.000082. This is only 15% of the efficiency 
obtainable for the sulfonated fluorocarbon ether catalyst as noted above, 
even though the temperature used in the Japanese patent is substantially 
higher where the efficiency would be expected to be greater. These 
comparisons illustrate that the present invention is decidedly superior.