CA1187106A - Process for preparing nonionic surfactants with narrow molecular weight distribution - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Process is provided for preparing nonionic surfactants having a narrower molecular weight distribution which comprises reacting a reactive hydrogen compound selected from the group consisting of monohydric alcohols having from 8 to about 20 carbon atoms, an alkyl substituted phenol, and a difunctional polypropylene oxide polymer having an average molecular weight in the range of 1000 to 5000 with an alkylene oxide having 2 to 4 carbon atoms at a temperature at which the reaction proceeds in the presence of at least a catalytic amount 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 converted to said basic salt in situ in the reaction mixture.

Description

12,555 ~ ~7~6 BACKGROUND OF ~HE INVENTION

This invention relates to ~he prepara~ion of improved nonionic surface active agents and, more par-ticularly, to a process for the oxyalkylation of certain reactive hydrogen compounds to prepare nonionlc surface active agents having a narrower molecular weight distribu-tion and lower pour points.
Condensation products of a single alkylene oxide, particularly ethylene oxide, or mixtures of alkylene oxides such as e~hylene and propylene oxide with an alcohol or al~yl phenol are well known in the art. The products are conven-tionally produced by reacting the reactive hydrogen compound with the alkylene oxidc in the presence of an alkaline or acidic catalyst. Such procedures result in the production of a mixture of condensation produc~ species containing alcohol or alkyl phenol derivatives wi~h different molecular proportions of alkoxyla~e. Thus, the reaction products gen-erally ob~ained are, in reality~ a mixture of derlvatives of the alcohol moiety having a wide range of alkylene oxide units presen~ 8S well as certain proportions of unreacted alcohol. Moreover, the conventional designation of an alcohol alkoxylate is of the average number vf alkylene oxide units present per molecule and there are substantial proportions of alcohol alkoxylate molecules present which have a greater and a lesser num~er of alkylene oxide ~nits present than ~he aetual average value would indicate It is generally desirable ~o restri~t the molecular distributi.on of the mixture ~o adjarent analogues o:E ~he desired product, insofar as possible, but this is qui~e

2.

~87~ 12,555 difficult to control. ~cidic catalysts tend to give a narrower molecular distribution than alkaline catalysts, but also contribute to ~he formatiorl of undesired by-products.
Thus, alkaline catalysts are genera~ly used as the ~nore eEficient type of catalyst but the molecular distribution in the resulting products are more diffuse.
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 units, 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 fluo~orate 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 U.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 convention-ally produced ethoxylate mixture using vapor phase separation techniques; in U.S. Patent 2,~70,220 to Carter, a two-stage process is disclosed for preparing ~onoalkyl ethers of ethylene glycol and polyethylene glycols of more restricted molecular weight range wherein an alkanol and ethylene oxide is related in the presence of an acidic catalyst during the first stage and t~en in the second-stage~ after removal of acid catalyst and unreacted alkanol, reacting the mixture ith ethylene oxide in the presence of an alkali metal alcoholate of the initial alkanol; and in U.K. Patent 1,501,327 12,555 ~ ~ ~ 7 ~ ~ ~

to Laemmle et al is disclosed a method of preparing mono-and poly-glycol ethers subs~an~ially free of undeslred alkylene glycols by-product~ wh~ch involves heating a react~on mixture containing an alkylene oxide and an alcohol in the presence of a catalyst conta~ning alkall or alkal~ne earth cations wherein some or ~11 of the catalys~
is an anhydrous high boillng liqu~d residue prepared by concentrating the liquid residue left from the same or diferent etherificaeion process aft r removal of the glycol ether product from the reaction mixture. To the best of our knowledge, however, none of the processes or special catalysts disclosed in the art are cQmple~ely satisfactory in that they require multi-stage procedures or special acid-resistant equipment, give undesirable by-products or simply do not provide suficient control over the molecular weight distribution. It would be highly desirable, therefore 3 to develop a process wherein the reaction of an epoxide with an alcohol could be more readlly carried out to prepare surfactant products ~ha~ have ~ narrow molecular weight distrlbution of ~nologue species and contain only small amounts, at most, of undesirable poly(alkylene glycol) and e~her by-prod~ces~

In accordance with the pre~ent inven~ion there is provided a process for the preparation of nonionic surfac-tants having a narrower molecular weight distribution which eompri~es reacting a reactive hydrogen compound selec~ed from the group ronsisting of monohydric alcohols havin~
from 8 to abou~ 20 oarbon atoms, an alkyl substîtuted phenol, and a dlfllr~c~iorlal polypropylene oxide polymer having ~n ~verage mo1ecu1ar weight in thP range of 1000 ~o ~7~ 12,555 5000 with an alkylene oxide having 2 to 4 carbon atoms at a temperature at which the reaction proceeds in the presence of at least a catalytic amount of a hasic 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 converted to the soluble basic salt in situ in the reaction mixture.
It has been discovered that the soluble basic salts of an alkaline earth metal as herein described not only cata-lyze the reaction of the active hydrogen compound and alkaline oxide but also favor a narrower molecular distribution, i.e., a more limited range of molecular species and a lar~er pro-portion of the desired species in the reaction product. More-over, 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 THE INVENTION
In the process of the invention, a reactive hydrogen compound selected from the group consisting of monohydric alcohols having from 8 to about 20 carbon atoms, an alkyl substituted phenol, and a difunctional polypropylene oxide polymer having an average molecular weight in ~he range of 1000 to 5000 is reacted with an alkaline oxide having 2 to 4 carbon atoms in the presence of a catalytic amount o a basic salt of an alkaline earth metal selected from the group consis~ing 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 ~ ~ ~ 7 ~ ~ ~ 12,555 from the group consi~ing of calcium, strontium, barium and mixtures of ~he same which may or may not be soluble in said reactants and i~ converted to the soluble ba~ic salt in ~itu ~n the reaction m~xture.
The reaction may be conducted in a conventional manner, that ~s, the reactive hydrogen compound and the catalys are placed in a reactor, alkaline oxide is added at the reaction temperature until the desired number of moles ha~e been added, and the product is removed from the reactor and n~.utralized. The reaction may he conducted in the pre-sence of a solvent, but u~ually a solvent i8 not employed.
The temperature at which the react~on proceeds is not narrowly critical and generally products can be made at a reasonable ra~e of reaction and without decomposltion of the reactants or reactlon products at a temperature be~7een about 50C. and 270C. with a temperature between about 100C. and 200C. being generally preferred. Whlle the pressure of the reaction ix not narrowly critical when low~boiling epoxldes~ s~ch as ethylene ox~de and propylene ox~de are employed, a pressurized reactor is preferably used.
The product may be neutralized with any acid tha~
will con~ert the catalyst to a neu~ral salt9 as for example~
acetic ac~d, carbon dloxide3 sulfuric acid, phosphorlc acid and phenol.
Sultable alcohols sre pr~mary and secondary aliphatic alcohols which are straight or branched chaln alld have fr~m elght ~o abou~ twenty carbon s~oms~ Exemplary of sueh ~uitable pr~mary straight chaln a~lpha~ic alcohols are n~oc~anol, n~nonallol3 n~decanol9~ undecanol~ n dodecanol~
~-~rldecanol 9 n~etr8dec~nol 9 ~pentadeconal, n~hexadecanol, 12,555 n~heptadecanol n-octadccanol, n-nonadecanol and eicosanol, and of such branched chain alcohols are 2-methyl-1-nonanol 2-me~hyl-1-undec~no~ 2-methyl-1-dodecanol, 2-methyl-1-tetra-decanol and the llke. Examplary secondary aleohols include 2 octano~ 2-dodecanol, 4-tetradec~nol, 6-heptadecanol, and the like. Mixtures of such alcohol~ lncluding cG~mereially available alcohols which normally comprise mixtures of alcohol are also ~uitableO Particularly preferred are linear and branched pr~mary alcchols and alcohol mixtures such as are produced by the "Oxo" reaction of normel C3-C20 olefins.
The proce~s of the inven~ion is also applicable to alkylphenols that are aliphatic~aromatic compounds hav-ing 12 to 22, and preferably 14 to 18 carbon atoms including, or example, compounds having alkylphenyl, alkenaphthyl, alkoxyphenyl and alkylcyclohexyl radicals that may contain conventional substituents such as hydroxyl groups, halide atoms, or alkyl side-chains. Exe~plary of such compounds are nonylphenol and dinonylphenol, Also suitable are difunc~ional propyl~ne oxide polymers having a molecular weight o 1000 to 5000, and preferably 1700 to 4100. The propylene oxide polymers hav-ing a molecular ~eight of 1000 to 5000 contains from 17 to 86 oxypropylene units in the molecule~ These compounds are well known being generally obtained by polymeriæation of propylene oxide or by the addi~ion o propylene oxide to lower molecular compounds wi~h 2 ~o 6 earbon atoms con-taining at lea~t 2 rea~tive hydrogen atoms~
Alkylene oxides 6ui.table for use in accordance with the invention have from 2 ~o 4 carbon atoms and

3~ include, for ex~ple 9 ethylene ox~de, 1,2=propyLene oxide, 1,2~butyle~e o~ide, and ~ xture~ thereof.
The num:bcr of mole~ of lkylene oxi.des emp~yed according ~o ~he pre~ent invention may vary w.ldely depending on the ~ 12,555 reactive hydrogen compound to be adducted and the particular application for which the ~urface active agent is to be employed. In general 2 to 60 and even more moles of alkylene oxide per mole of reactive hydrogen compound may be u~ed. Inso-fsr as propylene oxide and/or butylene oxide are u~ed in com-bination with ethylene oxid~, ~he molar ratio to ethylene oxide to propylene - or butylene oxide may bP from 1:0.03 to 1:1.
In the proce~s of the inven~ion, the reaction of an alkylene ~xide with a reactive hydrogen compound is catalyzed by the presence of 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 are soluble in the reactants and the reaction products produced thereby. Thesesui~able soluble basic alkallne ear~h metal sal~s may be c~lcium, strontium, and barium alkoxides and phenoxldes, preferably having alcohol and phenol moieties thereof which are the same or s~milar to the reactive hydrogen compound c~mponent of the oxyalkylation reaction, or soluble basic alkaline earth metal salts that are prepared in situ during the oxy~lkyla-20 tion reaction While basic salts of alkaline earth metals that aresuitable for use in accordance with ~he invention may be pre-pared by methods known in the ar~, a particularly preferred basic salt for use as a catalyst in the invention is prepared by the method of Canadian-~ applieation Serial No. 359116 wherein calcium, stron~ium nd barium alkoxides h~ving an alcohol moiety thereof that is ~he &ame or ~imilar to ~he alcohol reactlve hydrogen compound compon2nt ~re disclosed.
Such metal alkoxides are, in general, prepared by a two ~tep proce~s. In the first ~tep of ~he proce~s, for ,~

12,555 example, calcium, stronti~m and bari~ con~aining raw materials such a~ calcium, strontium, and barium metal, or hydrides or acetylid~s ~re reacted with a lower aliphatic alcohol having from about 1 to about 7 carbon atoms. The concentration of metal in the lower alcohol may v~ry from 0.01 to 20 percentO In the ~econd step, ~he l~wer aleohol metal alkoxide reaction product is mixed with an alcohsl h~ving at lea~ 4 carbon ~tom~ ~o form the alkaline earth metal alkoxide thereof. The basic alkaline earth alkoxide prepared thereby preferably has an alcohol moiety whlch is the same or similar to the reactive hydrogen comyonent used in the oxy-alkylation r~action mixture. The lower alcohol (alcohol having 1 to 7 carbon atoms) introduced with the lower metal alkoxide ls removed from the final metal alkoxide reaction product by any separation means that rPtains the cataly~ic ac~ivity of the alkaline car~h metal alkoxide, ~ith dis~illa-tion being generally preferred.
Alternatlvely, ~he alkaline earth metal alkoxide of lower alcohol prepared in the first step may be added to a reaction mixture comprising a reacti~e hydrogen compound and alkylene oxide wherein, for example, the reactive hydro-gen cv~pound is a monohydric alcohol having from 8 ~o abou~
70 carbon atoms and a soluble basic sal~ of the lkaline earth me~al formed in itu ha~ the catalytic activity desired.
ThR amount of c~aly~t used in accordanee ~ith ~he inventi~n is no~ narrowly crit~oal nd ~ catalytic effect has been noted wlth only a ~m~ll amount thereo being presen~. IR general the Ca~a1Y5~ concentratlon can vary from 0.001 percen~ by weight ~o 10 percent by weight of o~lcium, ~trsntium, and bar~um based on the welgh~ of ac~ive 1 ~ ~ 7 ~ ~ ~ 12,555 hydrogen compound. Concentrations of alkaline earth metal within the range from about 0.05 percent to about 5.0 percent by weight of active hydrogen compound are usually preferred, The reaction r2te, however, is dependen~ on both temperature and catalyst concentration and to achieve a given rate, more catalyst is regAuired at a low temperature than at a hlgh ~emperaeure.
The inven~ion ~ill b~come more clear when considered together with the following exa~ples which are ~et forth as being merely illustrative of the inYention and which are not intended, in any manner, to be limi~ative thereof.
Unless otherwise indicated, all parts and percentages are by weight.
~XAMPLE 1 - A mixture of 25 grams (0.19 moles) of calcium ethoxide (prepared by ~he reaction of calcium metal and ethanol) and lQ00 grams (4.7 moles) of a mixture of C12 to Cls primary alcohols (60% branched, 40% normal isomer~) available under the ~radename LIAL-125 from Liquichemica It~lia was heated at 90C under high vacuum in a ~irred flask distilling off ~he e~hanol and then transf@rred to a steel, 2.5-gallon au~cclave equipped with a stirrer, an automatic temperature controller, and an automatic feed controller. The autoclave wa~
heated tc 110C, pre~surized to 20 p~ig with nitrogen and then ~o 60 psig w~th ethylene oxide. By automatic co~trol, 1685 gr~m~ ~3803 mole~ of ethylene oxide was fed to the autoclave at 110C over a period of 2 1/2 hours. After cookout to 33 pslg, the product ~2717 gram~) w~ cooled, dra~ned rom ~he re~c~or, and neu~rallzed ~o a pH of 7 wlth ace~io ~cid in ~ 3~irred fla~kO

1~ .

~ ~ ~ 7 ~ 2,555 In a ~econd run, 8.2 gram~ (0.15 moles) of pota8sium hydroxide in 1000 grams of the mixture of the C12 to C15 primary alcohols hereinabove described was charged into the 2.5-gallon autoclave and heated to 110~C under 60 p8ig pre~ure a~ in run 1. 1685 grams (38.3 le~) o ethylene oxide was ~hen fed to the auto-clave and reacted with ~he alcohol at 110C over a period of 0.65 hours. After cookout, the product (2707 grams) was cooled, drained rom ~he reactor and neutralized to a pH of 7 w~th ~ce~ic ~cid.
Gel permeat~on chrom~togrsphy~ ~ standsrd technique for determining the molecular weight distribu~ion of polymers and surfaetants was used to ev~luate the reaction products. A
comparis~n of the widths of gel permeation peaks a~ their half-heights, all run at constant conditions, is a measure of the relative broadness of the molecular weigh~ dis~ribution of the polymers or æurfactan~s. When the performance of the instrument is calibrated with standards of known molecular weights, i~ is possible to define the molecular weight range represented by the peak width at half height.
Gel permeation chromatography results on the products of run #l and ~2 hereof are repor~ed in Table I, below.

TABLE I
GEL PERMEATION CHROMATOGRAPHY RESULTS
~Peak Wi~. At MoIecuIar Weight Ran Catalys~ 95~ U_ID~ e~ At One-Half HPi~ht_ Basic Caloium Alkoxide (Run #1) 2.9 360 820 Potasxlum Mydroxide (Run j~2) 4.4 320-1000 The c2~alytic effect using ~he ba~ic calcium alkoxide 3~ and po~ssium hydroxide ~s apparent from ~he above result~O
Although the catalytlc actlvity of ~he basic cnlcium alkoxide 1~ le~x th~n th~t of po~aasium hydroxide, the more favorable molecular di~ribution o ~he reaction pro~uct~ o~alned with this ca~alys~ as compared to po~asslum hydroxide 1~ apparent.

'1'1 .

~ ~ ~7 ~ ~ ~ 12,555 Pour point (ASTM D-9766) and cloud point (ASTM
D-20 4, 1% solution) values were al~o determined for the products prepared in runs #l ~nd #2. The product of run ~1 using the basic calcium alkoxide catalyst had a pour point of ~3F and a cloud point of 60C, both of which values are more favorable ~han the pour point of 73DF and cloud point of 55C determined for ~he pro-duc~ produced in run ~2.
E$~MPLE 2 In a series of test runs, l-dodecanol was reacted with etllylene oxide in the autoclave reactor of Example 1 using the procedure of Example 1 to evaluate the catalysts noted in Table II, below. In each run, 500 grams (~.7 moles) of l-dodecanol containing 0~10 to 0.12 m~les per liter of catalys~ was charged to the auto clave reactor and reacted with approximat~ly S.7 moles oE ethylene oxide a~ 140C, except as noted, and ~ psig.
The products were neutralized with phosphoric acid, filtered, an~ analyzed, The analytical results arP reported in Table II and Tabl~ III, below.
The catalysts used were prepared as follows:
For the potassium cata`lyst, potassium hydroxide was added to l-dodecanol, and then water was removed at 110C and lOmm vacuum. For ~he calcium, ~trontium, and b~ri~m catalysts ~ the metal was fir~t reacted under re1ux w~h exce~ ethanol or methanol to m~ke a 0O5 mole per liter ~olution. The alko~ide ~olutl~ in lower alcohol (ethanol or methanol) was added to 1 dodecanol a~d ~he lower alcohol and any water preaent wa~ removed at 110C ~nd lOmm vacuum.

1~ .

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~7~6 12,555 TABLE III
.

GEL PE~MEA~ION CHROMATOGRAPHY R~SULTS
~ ~ Mo1ecular Concentration Peak Width At Weight Range At ~ ~lle One-Hal Height (cc~ One~Half Hei~ht Potassium 0.48 4.5 270-930 hydroxide Calcium 0.48 2.9 290-640 ethoxide I

Strontium 0.97 3.1 290-690 ethoxide Barium 1.51 3.3 280-690 ethoxide Calcium 0.48 3.3 280-690 methoxide The resu1ts show that so1ub1e basic salts of barium, strontium, and calcium cata1yze t~le oxyethylation of the mono-hydric ~lcohol to give re~ction products having a narrower mo1ecu1ar weight distribution and lower pour points compared to products made with potassium hydror~ide.

~ 4.

~8~ 12,555 Run #l: 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 where 770 grams (17.5 moles) of ethylene oxide were added, and, using the procedure of Example 1, reacted at 140DC and 60 psig. After completion of the reaction, a portion of the product (507 grams) was removed from the autoclave and neutralized wi~,h acetic acid. Gel permeation chromatography results for 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 remov2d from the ~uto-clave and neutralized. The molecular ~eight 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 100C and high vacuum and then charged to the autoclave. Ethylene oxide (757 grams - 17.2 moles) 15.

~7~ 12,555 was reacted with the charge in the autoclave at 140C
and 60 psi~. After completi~n 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 140~C 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
Peak Width Molecular Wt.
At One-Half Range One-Catalyst Height (cc) Half Height 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 molecular wPight distribution of the reaction products as compared to potassium hydroxide was very favorable.

1~ .

12,555 -A mixture of 150 grams of barium ethoxide (pre-pared by the reaction of barium metal and e~hanol Ln the proport1Ons of 0.60 mols Ba/1000 grams of ethanol) and 550 grams of nonylphenol (2.5 moles) ls he~ted at 110C
under high vacuum to distlll off ~he ethanol. The soluti~n thu6 fonmed contains 0.16 moles Ba/1000 gm~
of organic compound (2.2 weight percent of barium3.
U~ing the autoclave reactor of Ex~mple 1, 500 grams ~2.3 moles of nonylphenol) of the nonylphenol solution prepared above is charged to the reac~o~ which is heated to 140C under 60 psig pressure, Over a period o 0.4 hour, 1062 grams (24 moles) of ethylene oxide is fed to the reactor. Af~er cookout to a cons~ant pressure (about 1 hour), the reaction mix~ure is cooled, drained from the reactor, n~utrali~ed, and analyzed. The catalyst compound is in solution with the reae~ion mixture ~ntil neutrali~ation.
The reaction product which is ~n ethylene oxide adduct of nonylphenol is determined ~o have a molecular weight of 682, a pour point of 4.3C and a cloud point (0.5% aqueous solution) of 65C.

17.

Claims (7)

WHAT IS CLAIMED IS:

1. A process for the preparation of nonionic surfactants which comprises reacting a reactive hydrogen compound selected from the group consisting of monohydric alcohols having from 8 to about 20 carbon atoms, an alkyl substituted phenol, and a difunctional polypropylene oxide polymer having an average molecular weight in the range of 1000 to 5000 with an alkylene oxide having from 2 to 4 carbon atoms 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 con-verted to said basic salt in situ.

2. The process of claim 1 in which said reactive hydrogen compound is a monohydric alcohol having from 8 to about 20 carbon atoms.

3. The process of claim 1 in which said soluble basic alkaline earth metal salt is selected from the group consisting of calcium, strontium, and barium alkoxide, calcium, strontium and barium phenoxide.

4, The process of claim 1 in which said soluble basic alkaline earth metal salt is selected from the group consisting of calcium, strontium, and barium alkoxide.

18.

5. The process of claim 1 in which said reactive hydrogen compound is a primary alcohol.

6. The process of claim 1 in which the catalyst concentration is within the range of 0. 001 percent and 10 percent by weight of alkaline earth metal based on the reactive hydrogen compound.

7. The process of claim 1 in which said alkaline oxide is ethylene oxide, propylene oxide, or mixtures of the same.

19.