CA1185992A - Process for the preparation of alkanol alkoxylates - Google Patents

Process for the preparation of alkanol alkoxylates

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Publication number
CA1185992A
CA1185992A CA 416773 CA416773A CA1185992A CA 1185992 A CA1185992 A CA 1185992A CA 416773 CA416773 CA 416773 CA 416773 A CA416773 A CA 416773A CA 1185992 A CA1185992 A CA 1185992A
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alkanol
component
process according
aluminium
ponent
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French (fr)
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Charles L. Edwards
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Shell Canada Ltd
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Shell Canada Ltd
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Abstract

A B S T R A C T

PROCESS FOR THE PREPARATION OF
ALKANOL ALKOXYLATES

Alkanol alkoxylates having utility, for example, as non-ionic surfactants in detergent formulations are prepared in accordance with the invention by the reaction of C6 to C30 alkanols with C2 to C4 alkylene oxides in the presence of a co-catalyst combination comprising as a first component one or more alkanol-soluble basic compounds of magnesium and as a second component one or more alkanol-soluble compounds of at least one element selected from the group consisting of aluminium, boron, zinc, titanium, silicon, molybdenum, vanadium, gallium, germanium, yttrium, zirconium, niobium, cadmium, indium, tin, antimony, tungsten, hafnium, tantalum, thallium, lead, and bismuth.

Description

PROCESS FOR THE PR~PARATLO~I OF
ALKANOL ALKOXYLATES

This invention relates to the preparatioll of alkanol alkoxylates by catalyzed addition reaction of alkylene oxides with alkanols.
Alkanol alkoxylates (or simply alkoxylates, as the ~ermi-nology is applied herein) are known mateLials havLng ~tllity, for instance, as solvents, surfactants, and chemical inter-mediates. Alkoxylates in which the alkyl group has a number of carbon atoms in the detergent range, i.e., from about 8 to 20, are common components of commercial cleaning formulations for in industry and in the home.
Under conventional practice, alkoxylates are typically prepared by the addition reac~ion of alkylene oxides with alkanols. As an illustration, the preparation of an ethoxylate by the addition of a number (n) of ethylene oxide molecules to a single alkanol molecule may be represented by the equation o R - OH + n H2C ~ H ~ R - o--4CH2 - CH2 - O~~nH, where R is an alkyl group and n is an integer equal to or greater than one.
Alkoxylation reactions between alkylene oxides and alkanols are known to be necessarily carried out in the presence of a catalyst, which may be either of acidic or basic character.
Recogni~ed in the art as suitable basic catalysts are the soluble basic salts of the alkali metals of Group I of the Periodic Table, e.g., lithium, sodium, potassium, rubidium, and cesium, and the soluble basic salts of certain of the alkaline earth metals of Group II of the Periodic Table, e.g., barium, strontium, and calcium. With regard to the basic salts of ~, magnesium, however, the most relevant teachings of the art, specifically those of U.S. Patents ~ioS. 4,239,917, 4,210,764 and 4,223,164, indicate that such magnesium compounds do not effectively promote the alkoxyla~ion of detergent range alkanols under basic reaction condi~ions.
The use of acidic catalysts for ~he alkoxy]atlon reaction is also known, including broadly, the l,ewis acld or ~r~edel-Crafts catalysts. Specific examples of these catalysts are the fluorides, chlorides, and bromides of boro1l, antimony, tungsten, iron, nickel, zinc, tin, aluminium, tltanium and molybdenum. The use of complexes of such halides with, for example, alcohols, ethers, carboxylic acids, and amines have also been reported.
Still other examples of known acidic alkoxylation catalysts are sulphuric and phosphoric acids; the perchlorates of magnesium, calcium, manganese, nickel and zinc; metal oxylates, sulphates, phosphates, carboxylates and acetates; alkali metal fluoroborates;
zinc titanate; and metal salts of benzene sulphonic acid. With specific regard to aspects of the process of the invention, while the art teaches alkoxylation catalyzed by a variety of acidic compounds of transition metals and metals of Groups III~
IV and V of the Periodic Table, there is no suggestion of any possible use of co-catalyst combination of acidic and basic compounds or the application of such acidic compounds as alkoxylation catalysts under basic reaction conditions.
Alkanolic solutions containing both basic magnesium compounds and compounds of certain transition metals are known (see e.g. U.S. Patent No. 4,178,300), but there has been no suggestion that they might be useful in promoting ethoxylation reactions.
In preparation of the alkoxylates by the addition reaction between alkanols and alkylene oxides, there is obtained as product a mixture of various alkoxylate molecules containing differing numbers of alkylene oxide moieties.
It is known that alkoxylate products having a narrow range distribution of numbers of alkylene oxide moieties per molecule ~ J~

("narrow-range alkoxylates") are preferred for use in detergent formulations. (see e.g. U.K. Pacent Specification No. L,462,134;
Derwent Publications Research Disclosure ~lo. 194,010.) Narrow-range alkoxylates are also known to be partlcularly valuable as chemical intermediates in the synthesis of certain carboxy-alkylated alkyl polyethers (U.S. Patent No. 4,098,818) and of certain alkyl ether sulphates (U.K. Patent Specification No.
1,553,561).
Conventional alkoxylation reactions promoted ~ole:L~ by the Lewis acid or Friedel-Crafts catalysts yielcl products hav-ing very desirable, narrow-range distributions of alkylene oxide adducts. However, the use of acid catalysts has processing disadvantages. For instance, the acid catalysts catalyze side reactions to produce relatively large amounts of polyalkylene glycols, and also react directly with components of the alkoxylation mixture to yield organic derivatives of the acid catalysts. Furthermore, efficient use of the acid catalysts is generally limited to the preparation of alkoxylates having an average number of alkylene oxide moieties no greater than about

2 or 3.
While conventional base-catalyzed alkoxylation reactions typically result in acceptably low levels of by-product formation and are not limited to the preparation of lower alkylene oxide adducts, they are known to produce only relatively broad-range alkoxylate products. It has recently been reported in the art (see e.g. ~.S. Patents Nos. 4,210,764, 4,223,164 and 4,239,917, and the European Patent Applications Publication Nos. 0026544, 0026546 and 0026547) that alkoxylation promoted by basic barium, strontium, and calcium compounds yields an alkoxylate product having a narrower range distribution of numbers of alkylene oxide moieties per molecule than that of products of alkoxylation catalyzed by basic compounds of the alkali metals, particularly potassium and sodium. Nevertheless, the products of all such base-catalyzed alkoxylation reactions are of substantially broader range distribution than is 5~

desirable or is obtainable in conventional acid-cataL~Jzed reactions.
It has now surprisingly been found that certain alkanol alkoxylates may be prepared by the addition reac~ion of alkylene oxides with alkanols carried out in the presence of a co-catalyst combination comprising both (a) one or more alkanol~
soluble basic compounds of magnesium and (b) one or more aoluble compounds of certain specific transition metals or e1ements selected from Groups III, IV, and V of the Periodic Table.
Neither component (a) nor (b) alone has been found to exhibit appreciable catalytic accivi.ty for the desired reaction.
According to the present invention there is provided a process for the preparation of alkanol alkoxylates which comprises reacting at least one alkanol having from 6 to 30 carbon atoms with at least one alkylene oxide having from 2 to 4 carbon atoms, in the presence of a co~catalyst combination comprising as a first component at least one alkanol-soluble basic compound of magnesium and as a second component at least one alkanol-soluble compound of at least one element selected from the group consisting of aluminium, boron, zinc, titanium, silicon, molybdenum, vanadium, gallium, germanium, yttrium, zirconium, niobium, cadmium, indium, tin, antimony, tungsten, hafnium, tantalum, thallium, lead and bismuth, the second component being present in an amount of at least 5 per cent by mol calculated on mols of first component.
The process of the invention is preferably carried out at a temperature in the range from 90 to 250C. A more preferred range is that from 130 to 210C, while a temperature from 150 to 190C is still more preferred. Considered most preferred is a reaction temperature in the range from 165 to 175C. Although the pressure under which the alkoxylation reaction is conducted is not critical to the invention, a total pressure in the range from atmospheric pressure to 106 Pa (gauge) (150 psig) is preferred. Under preferred conditions of temperature and pressure, the alkanol reactant is generally a liquid and the alkylene oxide reactant a vapour. The al~oxylatlon is then conducted by contacting gaseous alkylene oxide witll a liquid solution of the catalyst in the alkanol. Since, as is kno~m, there i9 ~ danger of explosion in alky]ene oxides malntained in concentrated form at elevated temperàture and pressure, the partial pressure of the alkyle~e oxide in the vapour phase is preferably limieed, for ins~.ance, to less than 4 x 105 Pa (60 psia), and ehls reactant is diluted with an iner~ ~as such as nitrogen, for instance, to a vapour phase concentration of 50 per cent or less. The reaction can, however, be safely accom-plished at greater alkylene oxide conceneration, greater total pressure and greater partial pressure of alkylene oxide if suitable precautions, known to the art, are taken to manage the risks of explosion. A total pressure of from 2.8 to 7.6 x 105 Pa (gauge) (40 to 110 psig), with an alkylene oxide partial pressure from 1 to 4 x 105 Pa ~15 to 60 psia), is particularly preferred, while a total pressure of from 3.5 to 6 x 105 Pa (gauge) (50 to 90 psig), with an alkylene oxide partial pressure from 1.4 to 3.5 x 105 Pa (20 to 50 psia) is considered more preferred.
Primary alkanols are particularly preferred alkanols having from 6 to 30 carbon atoms, largely on the basis of rate of the alkoxy].ation reaction. For reasons relating to the utility of the product alkoxylates in detergent formulations, preference may be expressed for alkanols within further restricted carbon number ranges. Thus, alkanols in the C7 to C22 range are preferred reactants, while those in the C8 to C18 range are considered more preferred and those in the C10 to C16 range most preferred. Still further preference for reason of product utility mag be stated for alkanol reactants in which greater than 50 per cent, more preferably greater than 70 per cent, and most preferably greater than 90 per cent of the alkanol molecules are of linear (straight-chain) carbon structure. Mixtures containing a variety of such alkanols, differing, for instance, with respect to carbon number and branching in the carbon chain, r3~

are of course suitable for purposes of the process of the invention and are in most cases preferred because of comMercial availability.
The alkylene oxides (epoxides) utilized i~ the process of the invention include ethylene oxide, propylene oxide, and the 1,2 and 2,3-buty]ene oxides. Particularly preferred are eth~lene oxide and propylene oxide, while the uYe of ethylene oxide is most preferred. Mixtures of alkylene oxides are suitable, in which case the product of the invention w:ill be a mixed alkoxylate.
The first component of the co-catalyst combination is either a basic compound of magnesium (which is directly alkanol-soluble) or a precursor which interacts with the alkoxylation process reactants to bring the magnesium into solution in a ]5 soluble basic form. The first component is described as soluble in the sense that it must be soluble in the liquid alkanol reactant (and, as the reaction proceeds in the liquid mixture of alkanol reactant and alkoxylate product) to the extent necessary to promote the desired reaction. (Magnesium metal, magnesium oxide, and magnesium hydroxide, heretofore attempted for use as alkoxylation catalysts, are essentially insoluble in the C6 to C30 alkanols at temperatures suitable for the invention and thus are not directly suitable for purposes of the invention.) This component is described as basic in the conventional sense, ~5 indicating that a hydrolyzed sample of an alkoxylation reaction mixture containing the magnesium compound in a catalytically-effective quantity (e.g., a 10%w solution of the reaction mixture in water) has a pH greater than 7Ø Examples of specific soluble, basic compounds suitable as the magnesium compound for the first co-catalyst component include the reaction products of magnesium with various alcohols (e.g., alcoholates such as the magnesium alkoxides and phenoxides), as well as ammoniate, amide thiolate, thiophenoxide and nitride compounds. Preferred for use as this catalyst component are the alcoholates, while the

3~

alkoxides in particular are considered more preferred Each alkox~ group of ~such alkoxides has a carbon number that is preferably in the rarlge from 1 to about 30, more pre~erably irl the range from l to 6. Most preferred are the CL to C3 alkoxldes, i.e. the methoxides, ethoxides and propoxides. Rep~esentative of suitable catalyst precursors which are converted into soluble, basic compounds of magnesium in the alko~ylation reaction mixture are the thiocyanates and the carboxy~a~es, such as the formate, acetate, oxalate, citrate, benzoate, laurate and stearate.
The magnesium-containing first component of the co-catalyst conbination is necessarily present in the reaction mixture in a co-catalytically-effective amount, typically of the order of at least 0.1 per cent by mol (%m), calculated on mols of the alkanol reactant. Preferably, the magnesium compound is present in a quantity from 0.2 to 20%m calculated Oll alkanol, while from 0.5 to 15%m is more preferred and from 1.5 to 10%m is considered most preferred. As a rule, the rate of the alkoxylation reaction increases as the invention is carried out with increasing quantities of this catalyst component.
The second component of the co-catalyst combination is preferably an alkanol-soluble compound of at least one element selected from the group consisting of aluminium, boron, zinc, and titanium. Compounds of boron or aluminium are particularly preferred, while aluminium compounds are considered most preferred.
The second component of the co-catalyst combination is either a compound which is directly alkanol-soluble or a precursor which interacts with the alkoxylation process reactants to bring the specified element(s)into solution. This co~ponent is described as soluble in the sense that it is soluble in the liquid alkanol reactant (and, as the reaction proceeds in the liquid mixture of alkanol reactant and alko~ylate product) in a co-catalytically-effective amount.
Examples of specific soluble compounds suitable as the second 3~

catalyst component include the reaction product.s of the specified metal with various alcohols (e.g., alcoholates such as the aluminium and boron alkoxides and phenoxides), a~s well as ammoniate, amide, thiolate, thiophenoxide and nitride compounds.
Preferred for use as this catalyst component are the alcoholates, ~hile the alkoxides in particular are considered more preferred. Each alkoxy group of sllch alkoxides has a carbon number that is preferably in the range Erom 1 to about 30, more preferably in the range from 1 to 6. Most preferred are the ethoxides and propoxides. ~epresentative of suitable catalyst precursors which are conver~ed into soluble compounds in the alkoxylation reaction mixture are the thiocyanates and the carboxylates, such as the formates, acetates, oxalates, citrates, benzoates, laurates, a'nd stearates.
lS It is thus preferred that the first and second components are independently selected from the group consisting of alkoxides having from 1 to 30 carbon atoms, more preferably 1 to 6 carbon atoms.
Particularly advantageously the first component is at least 2Q orle compound selected from magnesium methoxide, magnesium ethoxide and magnesium isopropoxide, and the second component is at least one compound selected from aluminium ethoxide and aluminlum propoxide.
The second component is preferably present in solution in the reaction mixture in an amount of at least 6 percent by mol (%m), more preferably at least 8%m, and most preferably at least 10%m, calculated on mols of the first component. As a rule, no further increase in activity is observed as the relative quantity of the second component is further increased above 10%m, based on the first component, although a substantially greater relative quantity remains very suitable for purposes of the invention.
In addition to considerations of catalyst activity, the relative quantities of the t~o components of the co-catalyst are also found to have a critical influence on the production of alkoxylates characterized by a narrow--range d1strIbution of alkylene oxide adducts. In a particularly preferred embodiMent of the inven~ion, the alkoxylation is carried out in the presence of a quantity of the second co-cataIyst component which is at least 10%m, calculated on mols of the first co~ponent.
This limitation Oll relative quantlt~ of the two catalyst components results in a reaction of enhanced selectivit~, yielding an alkoxylate having a range of alkylene oxide adducts which is narrower than that associated with the products of alkoxylations conducted using conventional basic catalystss and also having the advantage of relatively low content (e.g., 2A0%W
or less) of residual, unreacted alkanol. A process ylelding a product having a low level of residual alkanol as well as a narrow-range adduct distribution is particularly desirable, since it may eliminate the need for separation of the residual alkanol from the alkoxylate prior to use of the alkoxylate in many conventional applications. The narrow-range character of the distribution and the low level of residual alkanol are enhanced by further increase in the molar ratio of the second catalyst component relative to the first above 10~m. From the standpoint of this aspect of the invention, the quantity of second component for purposes of this alkoxylation process is preferably at least 12%m, more preferably at least 15%m, and most preferably at least 20%m, calculated on mols of first component present in the reaction mixture.
No upper limit has been observed for a suitable amount of the second co-catalyst component relative to the first. However, it is considered particularly desirable that the alkoxylation reaction of the process of the invention be carried out in a reaction nixture of overall basic pH. Commonly, although not necessarily, soluble compounds of the metals specified for the second co-catalyst component are of acidic character. For this reason the use of an amount of the second component that is not more than 100%m, calculated on the first is preferredO A quantity 3~

-- LO --of second component up to SU%m is more preferred and a qua~tity of up to 25~m is most preferred.
The relative selectivity of an alko~ylation process fo-r a narrow-range product can be quantltatively expres~sed in terms of an index value (Q), calculated accordlng to the equation Q = n p2 wherein n is a mean average adduct number, determined as the ratio of the total mols of alkylene o~.ide reacted to form alkoxylate, to the total mols of alkanoL either unreacted or reacted to form alkoxylate, and wherein P represent6 the highest selectivity of the reaction (in per cent by weight) for alkoxylate product molecules having any slngle common adduct number. Thus, for example, if the reaction product contained 10 per cent by weight of alkoxylate molecules characterized by an adduct number of 5 and lesser quantities of molecules having any IS other single adduct number, then P for the reaction product would equal 10. Higher values of Q indicate a more selective process and a more narrow-range product. For the typical ethoxylate products of greatest commercial interest, con-ven~ional alkoxylation of alkanols promoted by the alkali metal-containing catalysts yields alkoxylates characterized by a value for Q of approximately 500, while a conventional reaction promoted by basic compounds of the alkaline earth metals barium, strontium, and calcium yield products characterized by a value for Q of the order of 1200. Under practice of preferred aspects of the invention, utilizing the two co-catalyst components in the minimum relative amounts specified above for narrow-range alkoxylate preparation, products may be obtained having ad-vantageous Q values of at least 1250.
In terms of processing procedures, the invention is preferably carried out by mixing the co-catalyst components with the liquid alkanol reactant and then contacting the resulting solution T~Tith gaseous alkylene oxide at the specified temper-ature and pressure. Preferably, the second co-catalyst component is put into solution in the liquid reactant phase in the specified quantity before the first co-catalyst component is s~

mixed with this liquid phase. If the first component is added to the alkanol reacta~t irl the absence of the second co~ponent, the resulting mixture may form a viscous gel. While subsequent addition of the second co-catalyst component acts to break this gel, gel formation leads to handling problems whLch can be avoided simply be reversing ~he order of the addition of the two catalyst components to the alkanol.
The process of che inverltion may conveniently be efected as follows. Following the preparation of a solu~ion of the two co-catalyst components in the a1kanol in the relative quantities herein specified, the solution is preferably brought to the desired temperature and, by addition o~ alkylene oxide preferably together with an inert gas, to the desired pressure. Alkoxylation typically commences after an induction period of a few minutes to a few hours. As the alkylene oxide is taken up in the reaction additional alkylene oxide is added, conveniently ac a rate which maintains an approximately constant reaction pressure. ~ddition of alkylene oxide and its reaction to alkoxylate is continued until the product reaches the average alkylene oxide adduct number desired for the particular process. Generally, although not necessarily, the invention is best utilized in the prepa-ration of alkoxylates having an average number of alkylene oxide moieties in the range of from 1 to 30, expressed in terms of the total mols of alkylene oxide reacted per mol of alkanol. For reasons relating to utility of the alkoxylate in the broadest commercial applications the process is continued to yield a product having a number of alkylene oxide moieties that is preferably between 2 and 20, more preferably between 3 and 15, most preferably between 4 and 12. The time required to complete a process in accordance with the invention, in the presence of the specified co-catalyst combination, is dependent both upon the degree of alkoxylation that is desired (i.e., upon the average adduct number of the product) as well as upon the rate of the alkoxylation reaction. This reaction rate is, in turn, dependent upon such parameters reaction temperature, pressure, 5~ 3~

and catalyst concentration in the ~eaction mixture. Under most preferred operating conditions, prepara~ion o~ an alkoxylate having an average number of alkylene oxide raoietfes o~ about 3 may typically be accomplished in 0.5 to 1 ~lour, while prepa-ration of a product having an average number of aLkylene oxidemoieties of about 12 would typically require 4 to 6 hours. T~lese reaction times are merely illustrative and can be substantially reduced by operation at the higher reactlorl temperatures ~Ind/or pressures, although o~ten at the expense of a Loss selectlvit7 in the utilization of the reactants to the desire~ alko~ylate products. Following the reaction process, the product mixture is usually neutralized by addition of an acid to convert the basic catalyst components to inaccive neutral salts. The choice of the acid used is not critical. Examples of suitable acids known to the art for this service include acetic acid, sulphuric acid, phosphoric acid, and hydrochloric acid. Acetic acid is generally preferred.
The invention is further illustrated by the following examples.

An alkoxylation process in accordance with the inv~ntion was conducted in a 300 ml stainless steel autoclave reactor. The alkanol reactant was a "NEODOL" 23 Alcohol (trademark), charac-terized as a mixture of primary, 80% linear (20% branched) alkanols containing twelve and thirteen carbon atoms (about 40%m C12, 60%m C13) produced by hydroformylation. Initially, the liquid alkanol reactant was dried to a water content about 40 ppm (as indicated by Karl Fischer water analysis) by sparging with nitrogen at 130C for 35 minutes. About 0.351 grams (1.75 millimols) of the second co-catalyst component, in this case aluminium isopropoxide, was dissolved in 65 grams (335 milli-mols) of the dried alkanol in a multineck glass round bottom flask at 130C. Then 2.0 grams (17.5 millimols) of the first co-catalyst component, in this case magnesium ethoxide, was dissolved in the alkanol solution, producing a clear, colour-3~

less, non-viscous llquid. The resulting solution of the two catalyst components in the alkanol was sparged with ~itrogen at 130~C for 30 minutes to remove any isoproyanol or ethatlol released by trans-alcoholysis reac~ion. The solution was then transferred to the autoclave under a nitrogen atmosphere, the system sealed, heated to 170C and pressurized with nl~rogen and alkylene oxide reactant, in this case ethylene oxide, to a total pressure of 4.8 x 105 Pa (gauge) (70 psi.g) (3.8 ~ 105 Pa (55 psia) nitr~gen and 2 x 105 Pa (30 psia) ethy1ene oxide). Alkoxylation (ethoxylation) commenced after an induction period of orle hour.
Temperature was maintained at 1~0C. Ethylene oxide was added to the reactor system upon demand, that is, to maintain approxi~
mately constant reaction pressure. About 96 grams (2.17 mols) of ethylene oxide was added over a three hour period. The reactor was then maintained at 170C for an additional 30 minutes without addition of further ethylene oxide, to consume unreacted ethylene oxide in the system. After cooling to 50C, the product mixture was transferred under nitrogen to a sample bottle and neutralized with acetic acid to a pH of 6Ø Analysis of the product by GC-LC techniques indicated an alkoxylate with a mean average adduct number of 6.6, containing 1.8% residual alkanol and 0.05%w polyethylene glycol. T~e ethylene oxide distribution for the product was characterized by an index value 0~ (as defined above) of 1325.
Comparative Example A
An alkoxylation process was attempted under the general procedures of Example 1. In this case, however, the process was carried out in the absence of any second co-catalyst component and thus not in accordance with the invention. A mixture of 65 grams of the dried alkanol reactant and 2.0 grams magnesium ethoxide was prepared and sparged with nitrogen for one hour at 130C. The mixture was then contacted with ethylene oxide in the autoclave reactor maintained under a temperature of 170C and a total pressure of 4.8 x 105 Pa ~70 psig) (3.8 x 105 Pa (55 psia) and 2 x 105 Pa (30 psia) ethylene oxide). No alkoxylation was observed to take place over a period of five hours.
Comparative Example B
An alkoxylation process was attempted under the general procedures of Example 1, but in the absence of any flrst co-catalyst component and thus not in accordance with the inventlon.
A mixture of 6~ grams (350 millimols) of the dried alkanol reactant and 1.0 grams (5.0 millimols) of aluminium Lso-propoxide was prepared and sparged with ~itrogen fo~ 30 minu~es at 130C. The ml.xture was then contacted with ethylene oxide Ln the autoclave at a temperature of L70C and a total pressure of

4.3 x 105 Pa (gauge) (70 psig) (3.8 x 105 Pa (55 psia) nitrogen and 2 x 105 Pa (30 psia) ethylene oxide). Alkoxylation was extremèly slow, with but 12.3 grams of ethylene oxide taken up during a f;ve hour reaction period, yielding a product mixture having a mean average adduct number of only 0.9 and a very high content of residual alkanol (37.4%w).
The second co-catalyst component alone does not, under these conditions, appear to be effective to catalyze the produc-tion of an alkoxylate having an appreciably greater average adduct number, even over much longer reaction times.
E~AMP~E 2 Again following the general procedures of Example 1, an alkoxylation process in accordance with the invention was carried out using magnesium ethoxide as the first co-catalyst component and titanium isoprop~xide as the second co-catalyst component. First the titanium isopropoxide (0.341 grams, 1.2 millimols) and then the magnesium ethoxide (1.37 grams, 12 millimols) were dissolved in 65 grams of the dried alkanol reactant. After sparging with nitrogen at 130C for 60 minutes, the contents were introduced into the autoclave. At 170C and 4.8 x 105 Pa (gauge) (70 psig) tota~ pressure (3.8 x 105 Pa (55 psia) nitrogen, 2 x 105 Pa (30 psia) ethylene oxide), ethoxylation commenced after a two hour induction period. A total 'r7~

of 34.1 grams of ethylene oxlde were taken up during the following three hours. The reaction mixture was neutralized at 25C with acetic acid to a pH of 7Ø The alkoxylate product had a mean average adduct number of 3.4 and a residual alkanol content of 8.2%w.
E ~PLE 3 The general procedures of Example 1 were repeated using 2.0 grams (17.5 millimols) of magnesium ethoxide as the first co-catalyst component, 1.2 grams (5.26 millLmols) of tri n-butyl-borane as the second co-catalys~ component, and 68 grams of the dried alkanol reactant. Under the same conditlons of temperature and pressure, alkoxylation commenced after a four hour induction period. Alkoxylation rate was similar to that observed in Example 2.
E~PLE 4 A series of experiments were conducted to illustrate the performance of the invention with respect to production of a narrow-range alkoxyla~e product.
For one experiment in accordance with certain preferred aspects of the invention, the gereral procedures of Example 1 were followed to prepare a solution of 2.0 grams (17.5 milli-mols) magnesium ethoxide and 0.880 grams (4.38 millimols) aluminium isopropoxide in 60 grams (309 millimols) dried alkanol reactant. The quantity of the aluminium isopropoxide second co-catalyst component was 25%m calculated on the quantity of the magnesium ethoxide first co-catalyst component.
Alkoxylation of the alkanol in the autoclaYe at 170C and 4.8 x 105 Pa (gauge) ~70 psig) total pressure (3.8 x 105 Pa (55 psia) nitrogen and 2 x 10 Pa (30 psia) ethylene oxide) commenced after an induction period of two and one half hours. During three hours of reaction, a total of 88 grams of ethylene oxide (2.0 mols) was taken up to yield, after ne~tralization with acetic acid, an ethoxylate product having an average adduct number of 6.7 and contalning only 1.0%w residual alkanol and 0.05~w polyethylene glycols. The ethylene oxlde adduct distribution of this product was characterized by an lndex value Q (as defined hereinabove) of about 1750.
The high degree of narrowness associated with the adduct number distribution of the product of ~his experiment, as indicated by the index value of 1750, is the direct result of the high molar percentage (i.e., 25%m) of the second co-catalyst component, relative to the first. In Example 1, where the molar percentage of the second co-eatalyst component was only 10%rn, calculated on the first, the resultlng product was characterized by an index value of only about 1325.
In comparison to conventional alkoxylation reactions catalyzed by alkali metal and alkaline earth metal catalysts, certain embodiments of the invention9 as represented by both Examples 1 and 4, result in products having a greater degree of narrowness in the al~ylene oxide adduct distribution. Ethoxylation reaction conduc~ed for comparison purposes in the presence of potassium hydroxide, barium ethoxide, and calcium ethoxide catalysts, under procedures essentially equivalent to those of Examples 1 and 4, resulted in products characterized by Q values of about 540, 1190 and 1220 respectively. Under these comparative experiments, residual unreacted al~anol levels in the products of 3.3%w, 2.0%w and 2.1%w respectively, were greater than the 1.8%w and 1.0%w levels in the products of Examples 1 and 4, respectively.

Claims (13)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of alkanol alkoxylates which comprises reacting at least one alkanol having from 6 to 30 carbon atoms with at least one alkylene oxide having from 2 to 4 carbon atoms, characterized in that reaction is effected in the presence of a co-catalyst combination comprising as a first com-ponent at least one alkanol-soluble basic compound of magnesium and as a second component at least one alkanol soluble compound of at least one element selected from the group consisting of aluminium, boron, zinc, titanium, silicon, molybdenum, vanadium, gallium, germanium, yttrium, zirconium, niobium, cadmium, indium, tin, antimony, tungsten, hafnium, tantalum, thallium, lead, and bismuth, the second component being present in an amount of at least 5 per cent by mol, calculated on mols of first component.
2. A process according to claim 1, wherein the second com-ponent is at least one alkanol-soluble compound of at least one element selected from the group consisting of aluminium, boron, zinc, and titanium.
3. A process according to claim 2, wherein the second com-ponent is at least one alkanol-soluble compound of at least one element selected from the group consisting of aluminium and boron.
4. A process according to claim 3, wherein the second com-ponent is at least one alkanol-soluble compound of aluminium.
5. A process according to claim 1, wherein the second com-ponent is present in an amount from 10 to 100 per cent by mol, calculated on mols of the first component.
6. A process according to claim 5, wherein the second com-ponent is present in an amount from 15 to 50 per cent by mol, calculated on mols of the first component.
7. A process according to claim 1, wherein the first and second components are independently selected from the group con-sisting of alcoholates, ammoniates, amides, thiolates, thiophen-oxides, nitrides, thiocyanates and carboxylates.
8. A process according to claim 1, wherein the first and second components are independently selected from the group con-sisting of alkoxides having from 1 to 30 carbon atoms.
9. A process according to claim 8, wherein the first and the second components are independently selected from the group consisting of alkoxides having from 1 to 6 carbon atoms.
10. A process according to claim 1 or 9, wherein the first component is at least one compound selected from magnesium methoxide, magnesium ethoxide and magnesium isopropoxide, and wherein the second component is at least one compound selected from aluminium ethoxide and aluminium isopropoxide.
11. A process according to claim 1, wherein the first com-ponent is present in an amount of from 0.5 to 15 per cent by mol calculated on the mols of the alkanol.
12. A process according to claim 1, wherein the alkanol has from 8 to 18 carbon atoms and the alkylene oxide is ethylene oxide.
13. A process according to claim L, wherein reaction is effected at a temperature in the range from 150 to190°C.
CA 416773 1981-12-23 1982-12-01 Process for the preparation of alkanol alkoxylates Expired CA1185992A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4727199A (en) * 1985-07-10 1988-02-23 Union Carbide Corporation Heterogeneous alkoxylation using anion-bound metal oxides
US4873017A (en) * 1985-07-10 1989-10-10 Union Carbide Corporation Heterogeneous alkoxylation using anion-bound metal oxides
US4892977A (en) * 1988-06-13 1990-01-09 Texaco Chemical Company Preparation of nonionic surfactants by oxyalkylation with a magnesium catalyst
US5012012A (en) * 1987-09-29 1991-04-30 Lion Corporation Alkoxylation catalyst
US5025094A (en) * 1985-07-10 1991-06-18 Union Carbide Chemicals And Plastics Technology Corporation Heterogeneous alkoxylation using anion-bound metal oxides
US5068456A (en) * 1988-06-13 1991-11-26 Texaco Chemical Company Preparation of nonionic surfactants by oxyalkylation with a phenolic activated magnesium catalyst
US5136106A (en) * 1985-07-10 1992-08-04 Union Carbide Chemicals & Plastics Technology Corporation Heterogeneous alkoxylation using anion-bound metal oxides

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4727199A (en) * 1985-07-10 1988-02-23 Union Carbide Corporation Heterogeneous alkoxylation using anion-bound metal oxides
US4873017A (en) * 1985-07-10 1989-10-10 Union Carbide Corporation Heterogeneous alkoxylation using anion-bound metal oxides
US5025094A (en) * 1985-07-10 1991-06-18 Union Carbide Chemicals And Plastics Technology Corporation Heterogeneous alkoxylation using anion-bound metal oxides
US5136106A (en) * 1985-07-10 1992-08-04 Union Carbide Chemicals & Plastics Technology Corporation Heterogeneous alkoxylation using anion-bound metal oxides
US5012012A (en) * 1987-09-29 1991-04-30 Lion Corporation Alkoxylation catalyst
US4892977A (en) * 1988-06-13 1990-01-09 Texaco Chemical Company Preparation of nonionic surfactants by oxyalkylation with a magnesium catalyst
US5068456A (en) * 1988-06-13 1991-11-26 Texaco Chemical Company Preparation of nonionic surfactants by oxyalkylation with a phenolic activated magnesium catalyst

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