CA1170665A - Process for reaction of epoxides with organic compounds having an active hydrogen - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A process is provided for the reaction of an organic compound having an active hydrogen such as alcohols, phenols, polyols, acids, and amines with epoxides in the presence of a basic salt of an alkaline earth metal selected from the group consisting of calcium, strontium, and barium which is soluble in the reactants and the reaction products to prepare products having a narrower molecular weight distribution.

Description

12,337 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.

iiJ~
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 ~ ~

12,337 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, 12,337 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 .
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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.

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:

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.

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.

.
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.

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12,337 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).

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.

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 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.

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_ .,,1_ V O O~ U~O O V0~ ~
t,~ ~ t`~ OC:~ Xt~l ~D t) ~D tO

~; ~ ~ ~o ~ ~ C O~
O C O

V P~`J ~~ ~~U~ ~ ~ ~ p.
1~ 00 00_1 0 0 ~ ~
~ ~ ~ ~ O
0~ ~ ~ V
":~ x ~ 8 e ~ .c K ~ U~ ~ ~O ~O v ~ C :~
~- O O ~~O K ~ ~ O
p~ ~K
.C ~ ~~ o v ~ ~ _~ ~ O
~J v J .C ~ ~ ~O .C 1~
~ ~ a v ~ ;.0v_ t~ ~ V~
0 ~ ~ U ~ U U
U U ~ ~ U U

.

~ v 12,337 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.

Claims (10)

12,337 WHAT IS CLAIMED IS:

1. A process for the reaction of an organic compound having an active hydrogen with an epoxide which comprises reacting 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 at a temperature at which the reaction pro-ceeds 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 converted to the soluble basic salt thereof in situ .

2. The process of claim 1 in which the catalyst is a soluble basic alkaline earth metal salt selected from the group consisting of calcium, strontium, and barium alkoxides, calcium, strontium, and barium amides, calcium, strontium, and barium phenoxides, and the mutual reaction product of a calcium, strontium, or barium hexammoniate, an olefin oxide and an organic nitride.

3. The process of claim 1 in which the catalyst is selected from the group consisting of calcium, strontium and barium alkoxides.

4. The process of claim 1 in which the catalyst concentration is within the range of 0.001 percent and 10 per-cent by weight of alkaline earth metal based on the active hydrogen organic compound.

27.

12,337

5. The process of claim 1 in which the organic compound is selected from the group consisting of monohydric alcohols, phenols, and polyols.

6. The process of claim 1 in which the organic compound is a monohydric alcohol having from one to about thirty carbon atoms.

7. The process of claim 1 in which the organic compound is a polyol having from two to about thirty carbon atoms and from two to six hydroxyl groups.

8. The process of claim 6 in which the catalyst is selected from the group consisting of calcium, strontium and barium alkoxides and mixtures of the same.

9. The process of claim 7 in which the catalyst is selected from the group consisting of calcium, strontium and barium alkoxides and mixtures of the same.

10. The process of claim 1 in which the epoxide is an alkaline oxide or mixtures thereof.

28.