CA1283092C - Heterogeneous alkoxylation using anion-bound metal oxides - Google Patents

Abstract

HETEROGENEOUS ALKOXYLATION
USING ANION-BOUND
METAL OXIDES
ABSTRACT OF THE DISCLOSURE

Active-hydrogen compounds, for example, primary and secondary alcohols or diols, are alkoxylated, for example, ethoxylated, using solid anion-bound metal oxide catalysts such as zirconium oxysulfate catalyst. Hydrous zirconium oxide is treated with solutions of sulfate, phosphate, nitrate or tetrafluoroborate and calcined in air at 300°C to 950°C to produce highly active heterogeneous alkoxylation catalysts. The amorphous catalysts afford narrow molecular weight products.
The catalyst can be removed from the product by filtration and reused with no significant loss in activity. Reaction temperatures of 50°C to 140°C
are employed for alkoxylation.

Description

~ 3~

HETEROGENEOUS_ALKOXYLATION USING
ANION-BOUND METAL OXIDES

BACKGROUND OF THE INVENTION

~ 1. Field Of The Inventlon : 5 The invention relates to a catalytic process of alkoxylating active-hydrogen compounds, to the starting compositions and to the alkoxylation catalysts.
:;

2. Background Art Hino, ~akoto, and Kazushi Arata, "Synthesis of Solld Superacid Catalyst with Acid 3trength of Ho <
-16.04", J.C.S. Chem. Comm., (1980) pages 851 and 852, discloses a solid superacid catalyst with an acid strength of Ho < -16.04. The catalyst was obtained by exposing Zr(OH)4, prepared by the hydrolysis of ZrOC12, : 15 to lN H2S04 and then calcinlng it ln air at 575 to 6500C.
Hino, Makoto, and Kazushi Arata, "Synthesis Of Esters From Acetic Acid With Methanol, Ethanol, Propanol, Bu~anol, And Isobutyl Alcohol Catalyzed By Solid Superacid", Chemical Letters, Chem. Soc. Jap., (1981), pages 1671 and 1672, discloses catalytically esterlYying acetic acid with lower alkanols, such as, .. ~

:~ .

:,.
. .
.,........ ~.~, :. :

5!33~

ethanol. A solid superacid catalyst, which was obtained by exposing Zr(OH)4 to lN H2SO4 and then calcining in ~ir at 500 to 750C " was stated to be highly active for the heterogeneous esterification reactions at 30 to 45C. The reactions with used catalysts gave identical results with those using freshly activated catalysts.
(Esterificatlon reactlons are known to be catalyzed by aclds.) Solid superacld catalysts were also prepared from ( )3 4 4 Hino, M., and K. Arata, "Conversion Of Pentane To Isopentane And Isopentane To Isobutane Catalyzed By A
Solid Superacid In The Vapor Phase"~ React. Kinct, Catal. Lett., Vol. 19, No. 1-2, (1982), pages 101 to 104, dlscloses converting pentane and isopentane, respectlvely, into isopentane and isobutane using a solid superacid, which was prepared by exposing Zr(OH)4 to lN H2S04, followed by calcination at 650C. ln air.
The selectivities were 84 percent under short contact conditlons at 80C. The reactions involved the isomerlzatlon and hydrocrack~ng o~ lower hydrocarbons.
The paper states that Takahashi et al. prepared solld superacids by supporting SbF5 on metal oxides and studied reactions o~ pentane and isopentane. [R.
Ohnishi T., Morikawa, Y. Hira~a and K. Tanabe, ` 25 Zeitschrif`t fur Physikalische Chemic Nue Folg, Vol. 130, ~:~3309;2 pp. 205-209, (1982)]
The above-dlscussed Hino and Arata articles are ~nconsistent and teach away from the invention which is the subJect o~ thls application.
Chukhlantsev, V.G., and Yu. M. Galkin, "Thermal Decomposition Of Baslc Zirconium Sulphate", Russian Journal of Inorganic Chemistry, 18 (6), (1973), pages 770 and 771, earlier disclosed that when basic zlrconlum sulphate ls heated to 500 to 650C. (even above 400 to 420C.) only dehydration, accompanied by the formation of an anhydrous product amorphous to X-rays, took place.
Starting from 600C. the latter decomposed with the formation of ZrO2 and release of SO3. Basic zirconium sulfate was obtained by boiling a solution of zirconium oxide chlorlde containing 50 g of ZrO2 per llter, 15 g of ~ree HCl per liter, and sulfuric acid to give SO3:
Zr2 = 0.56 (molar). The product was washed and then dried at 100C.
The Condensed Dictionary, 10th Ed., (1981) pages 1115 to 1117, dlscloses: Zr508(S04)2.xH2O, zirconyl sulfate on zirconlum sulfate, basic; ZrOCO3.xH2O, zirconyl carbonate or zirconium carbonate, basic;
ZrOC12.8H2O, zirconyl chloride or zlrconlum oxychloride;
ZrO(OH)Cl.nH20, zlrconyl hydroxychloride; and ZrO(OH)NO3, zirconyl hydroxynitrate or zirconyl nitrate, :, .

, . :

~.2~3~92 ~D 13928 basic. 2irconium oxychloride can be prepared by the action of hydrochloric acld on zlrconium oxide.
Z~rconyl sulfate can be prepared in a similar manner.
Zr(OH)4 can be prepared by the actlon of a solution o~
sod~ium hydroxide on a solutlon of a zlrconium salt.
Ethylene oxide, also termed oxirane, has been reacted with C2H50H to produce C2H50CH2CH20H. The same reaction with ethylene sulflde is known.

BROAD DESCRIPTION OF THE INVENTION

The invention involves the baslc and unexpected discovery that anion-bound zirconium oxides and certain other anion-bound metal oxides are heterogeneous catalysts for alkoxylation, particularly ethoxylation.
The invention process ls broadly the use of anion-bound metal oxide heterogeneous Gatalysts ~or the alkoxylation o~ active-hydrogen compounds, such as, primary or secondary alcohols and diols. Anion-bound zirconium oxide heterogeneous catalysts are highly active.
The invention process for the alkoxylation of ac~ive-hydrogen compounds includes reacting a liquid or solid reactive epoxide compound having the ~ormula:

09~ UD 13928 - o ~
I
RlR2C CR3R4 wherein Rl, R2, R3 and R4 are each H or -(CH2)nCH3, and whereln n is 0 to 3, with the proviso that Rl, R2, R3 and R4 can be the same or diff`erent, wlth an active-hydrogen compound, the active hydrogen compound belng in the llquid or gaseous state, in the presence of a catalytlc amount of at least one solld anlon-bound metal oxide catalyst. The anlon-bound metal oxlde catalyst ls an amorphous or primarily amorphous compound. The active-hydrogen compound ls one which does not polson the catalyst. The pre~erred active-hydrogen compound is preferably a primary monohydric alcohol, a secondary monohydric alcohol, a 15 dihydric alcohol, a trihydric alcohol, a polyhydric alcohol, an alkoxylated ethylene glycol or a glycol ether. Water can be used as the active hydrogen compound. The molar ratio o~ the cyclic epoxide compound to the active-hydrogen compound ls usually 20 between 3:1 and 1:3. The process ls especlally advantageous in the ethoxylation of ethylene glycol.
In the processes of the lnvent~on~ the preferred ',... .. , ''` -: .~,.. ...

-~2~330~3X

epoxide compound is ethylene oxide. Also preferably the reactlon ls continuously conducted in a flxed-bed r~actor or a fluidized reactor. Also in the processes of the lnvention, preferably 0.5 to 50 weight percent, bas~d on the total weight of the cycllc epoxide compound and the other reactant, or reactants, of the solid anlon-bound metal oxlde catalyst is used. Preferably the anlon in the anion-bound metal oxlde catalyst ls S0 BF4, C03, B03, HP04, SeO4, MoO4, B407 6 the metal oxlde in the anlon-bound metal oxide catalyst ls zirconium oxide, nickel oxlde, alumlnum oxide, tin oxide, magnesium oxlde, rubldium oxlde, tltanium oxide, thorlum oxide, hafnium oxide or iron oxide. ZrO wlll readlly blnd with anions other than S04; whereas the other metal oxides wlll readily blnd with S04 but not as ~ readlly with the other anions. Preferably the catalyst ; is a solld sulfate-bound zl~conlum oxide catalystJ a solid sulfate-bound thorlum oxide catalyst or a solid sulfate-bound hafnium oxide catalyst. Although not preferred, the reactants can be used in inert liquid diluents such as hydrocarbons. Normally, the catalyst can be reused with good selectivity. If necessary, the solld anlon-bound metal oxide catalyst can be removed from the-reaction site and can be regenerated by calcination in alr or oxygen at a temperature of 300 to . . . . .

~2~3~9~

950C. for a period of 1 to 4 hours.
An advantage of the invention process is that it pfoduces a narrow moiecular range of products with a minimum of undesirable high molecular weight co products or by-products.
The polyoxyethylation of an alcohol is a process of reactlng an alcohol with ethylene oxlde to produce a polyether, as in the reaction below, in whlch R of the alcohol can be aliphatlc or aromatic:

o / \
ROH + nCH2 CH2 - ~RO (CH2CH2O)nH

The number of moles (n) of ethylene oxide reacted can range from 1 to greater than 200. The reaction occurs by a stepwise addition of the polymerization process usually catalyzed by acids or bases. The average molecular welght of the product alcohols is determined by the moles of ethylene oxlde reacted compared to the moles of hydroxyl groups in the starting alcohol. The product can contain s~gniflcant amounts of unreacted starting alcohol, depending on the relative reactivity of the starting alcohol compared to the reactivity of the product alcohols. All unhindered hydroxyl groups of ' . ' ~ ' . .
'' g%

monohydrlc and polyhydric alcohols react, but some may be more reactive than others. The process temperatures u~ually range from 80 to 180C. with the pressure at a level (e.g,, 20 to 100 p.s.-l.g.) needed to maintain S co~ditions ln the reactor. Often an excess of alcohol and/or cyclic epoxlde iB used.
The invention also involves a composition containing (a) a liquid or solid epoxide compound having the formula:

R R C- ~ 3 4 wherein Rl, R2, R3 and R4 are each H or -(CH2)nCH3J and wherein n is 0 to 3, with the proviso that Rl, R2, R3 and R4 can be the same or di~ferent, (b) an active-hydrogen compound, such as, a secondary monohydric alcohol, a dlhydric alcohol1 a trihydric alcohol, a polyhydric alcohol, an alkoxylated ethylene glycol or a glycol ether, the active-hydrogen compound being in the gaseous or liquid state, and (c) a catalytic amount of at least one solld anion-bound metal oxlde catalyst. The anion-bound metal oxide catalyst is an amorphous or primarily amorphous compound. The ~28309;:
UD 1392a active-hydrogen compound ls one which does not poison the catalyst.
The inventlon further involves reacting at least one molecule of a liquid or solld epoxide compound havlng the formula:

RlR2C - ~ ~ CR R4 wherein Rl, R2, R3 and R4 are each H or -(CH2)nCH3, and wherein n is 0 to 3, with the proviso that Rl, R2, R3 and R4 can be the same or different, with at least one other molecule of the above-identified liquid or solid epoxide compound in the presence of a catalytic amount of a~ least one solid anion-bound metal oxide catalyst.
The molecules of epoxide compound can be the same epoxlde compound or different epoxide compouds. The anion-bound metal oxlde catalyst is an amorphous or primarily amorphou.s compound.
The invention still further involves a composition including (a) at least one liquid or gaseous epoxide , 20 compound having the formula:

.
.

. . " .

~L~83~9Z

r-- o~
1, 1 .

, RlR2C ---CR3R4 whereln Rl, R2, R3 and R4 are each H or -(CH2)r~CH3, and wh~rein n is 0 to 3, with the proviso that R1, R2, R3 and R4 can be the same or different, and (b) a catalytic amount of at least one solid anion-bound metal oxide catalyst. The anion-bound metal oxlde catalyst is an amorphous or primarily amo~phous compound.
The lnvention also lnvolves the alkoxylation process o~ reacting an epoxide compound having the formula:

, ---- O

RlR2C - - 3 4 wherein R1, R2, R3 and R4 are each H or -(CH2)nCH3, and wherein n is 0 to 3, with the proviso that R1, R2, R3 and R4 can be the same or different, with a sodium salt of an acid sulfate of a secondary monohydric alcohol havlng 10 to 20 carbon atoms, the secondary monohydrlc alcohol salt bein~ in the liquid state, in the presence of a catalytic amount o~ at least one solid anion-bound metal oxide catalyst. The anion-bound metal oxide 1~83~ UD 13928 catalyst is an amorphous or primarily amorphous compound. The molar ratlo of the epoxlde compound and t,he secondary monohydric alcohol salt is usually between 3:1 and 1:3.
The invention further involves the composltion comprised of (a) a liquid or gaseous epoxide compound having the fo~ula:

O_ 1 R R C ~ 3 4 wherein Rl, R2, R3 and R4 are each H or -(CH2)nC~3, and whereln n is 0 to 3, with the proviso that R1, R2, R3 and R4 can be the same or different, (b) a sodium salt of an acid sulfate of a secondary monohydric alcohol having 10 to 20 carbon atoms, the secondary monohydric alcohol salt being in the liquid state, and (c) a catalytlc amount of at least one solid anion-bound metal oxide catalyst, The anlon-bound metal oxide catalyst is an amorphous or primarily amorphous compound. The molar ratio of the epoxide compound and the secondary monohydric alcohol salt is usually between 3-1 and 1:3.
Another important aspect of the invention is that it encompasses solid anion-bound metal oxide catalysts which are: (a) sulfate-bound tin oxide catalyst, (b) l~æs;~g'~
~D 13928 sulfate-bound nickel oxlde catalyst, (c) sulfate-bound aluminum oxide catalyst, (d) sulfate-bound magnesium ~xide catalyst, (e) sul~ate-bound rubidium oxide catalyst, (f) sulfate-bound thorium oxlde catalyst, (g) ; sul~ate-bound hafnium oxide catalyst, or (h) an anion-bound metal oxide catalyst wherein the anion ls S04, BF4, C03, B03, HP04, SeO4, MoO4, B407 or P~6, and the metal oxide is an oxide of zlrconium, nlckel, aluminum, tin, magnesium, iron, titanium, thorium, hafnium or rubidium. The anion-bound metal oxide catalyst is an amorphous or primarily amorphous catalyst. The catalysts are useful in the above-described alkoxylation processes and in the processes set out in the above prior art section.

DETAILRD DESCRIPTION OF' T~E INVENTION

As used herein, all parts, ratios, percentages and proportions are on a weight basis unless otherwise stated herein or otherwise obvious herefrom to one skilled in the art.

The anion-bound metal oxide catalysts of the invention are heterogeneous catalysts, that is, they are useful in heterogeneous catalysis. Heterogeneous catalysis lnvolves a catalytic reaction in which the 33~9Z

reactants and the catalyst comprises two separate phases, e.g., gases over sollds, or liquids containing f,inely-divided solids as a disperse phase. (By way of contrast, homogeneous catalysls involves a catalytic reaction in which the reactants and the catalyst comprlse only one phase, e.g., an acid solution catalyzlng other llquid components.) The subJect alkoxylation reactions of the invention occur on the surface of the solid catalyst particles. The individual steps of heterogeneous catalytic processes probably involve the following:

(l) Diffusion of reactants to surface.
(2) Adsorption of reactants on surface.

(3) ~eaction of absorbed reactant to form adsorbed product.

(4) Desorption of product.

(5) Diffusion of product into main stream of a liquid or vapor.

The reaction rates of alkoxylation reactions were unexpectedly significantly increased by the solid anion-bound metal oY~ide catalysts of the invention.
While a catalytic amount of catalyst is to be used, preferably 0.5 to 50 weight percent of the cataly~st is ~;283(~

used based on the total weight of the reactants. Of course, higher levels of the catalys~ can be used and m~xtures of the catalysts can be used. One or more promoters can also be used.
~ One of the preferred anion-bound metal oxide catalysts is zirconlum oxysulfate catalyst. It provides a substantial lncrease of reaction rate in ethoxylatlons with excellent selectlvity. For example, the use of zlrconlum oxysulfate catalyst in the ethoxylation of ethylene glycol produces very little of the undesirable 1,4-dloxane.
Production of the catalyst involves, for example, reactlng a compound havlng an anion with the metal hydroxide, such as, Zr(OH)4, Zr(OH)4.xH20, Hf(OH)4, Fe(OH)3, Al(OH)3, Th(OH)4, Nl(OH)2, and Mg(OH)2. (Any other sultable method can be used to prepare the catalyst.) The metal hydroxlde can be produced by hydrolyzing metal oxy-anlon group compounds~ such as, ZrOC12.8H20, 3)2-2H20, Zr50g(S04)-xH20~ ZrO(C2H302)2 ZrOBr2.xH20, ZrOI2.8H20, ZrO5, HfOC13.8H20, ZrOOHCl.nH20, ZrO(OH)NO3 and ZrO(SO4). The hydrolysis can be achieved uslng a hydrolyzing agent, such as, ammonlum hydroxide, sodium hydroxlde, potassium hydroxlde, barlum hydroxide, lithium hydroxlde, : .

~283~ X

magneslum hydroxlde, Na2S04, (NEI4)2HP04 and so forth-Following hydrolysis, the solids are removed from the hydrolysis solutlon, usually by flltration, dried (at say 100C. or any other appropriate temperatu~es) and optionally particulated or powdered.
The metal hydroxide is t~eated with the reactlve compound containing an anlonic group under suitable conditions. The anion can be monovalent or divalent or have a highe~ valence. Examples of the reactive compounds having an anionic group are H2SO4, phosphoric acld, nltric acid, etc. Such acids are examples of the reactive compounds havlng an anionlc group, but Lewis acids can also be used as such reactive compounds ; having an anionlc group. A Lewis acid ls a substance 15 that can act as an electron-pair acceptor. Lewis acids include trivalent derivatives of boron and aluminum, as well as salts of many other metals. Examples of specific Lewis acids are BF3, BC13, AlC13, AlF3, FeC13, 4' 2' 1~ g 12~ AlH3~ PFs~ Sb~5 and S03.
If one starts with compounds such as ZrOS04 and TiOS04, the sulfate-bound metal oxide compounds can be p~epared dlrectly by adding the hydrolyzing agent (e.g., sodium hydroxide) to a solutlon of the ZrOSO4, TiOS04 or the like.
The solld anion-bound metal oxide catalyst ls 30~
~D 13928 normally dried (at 100C. or any other sultahle temperature) before belng calcined, The dryin~ step to be used ls any technique whlch sufficiently evaporates the volatile constituents of the impregnating solution.
Calcination of the anlon-bound metal oxlde catalyst can be done ln air or oxygen at a temperature of 300 to 950C., preferably 500 to 800OC., fo~ a suitable period of tlme. The calclnation is normally conducted for one to four hours, or more. Zirconium oxysulfate catalyst productlon preferably lnvolves calcination ~n air at a temperature o~ about 575C.
The calcined catalyst has lts water molecules removed by the calcination, so the calcined catalyst should be kept in an air tight container, such as, a desiccator, untll it is used.
The zirconium catalysts of the invention are not zirconyl salts, such as, zirconium oxysulfate. Instead, the zirconium catalysts of the invention are anion-bound zirconium oxldes. The anlon, for example, S04, bridges the zirconium oxide moieties. Examples of such anions are S04, BF4s C03, B03, HP04, SeO4, MoO4, B407 o~ PF6, and the metal oxide is zirconlum, nickel, aluminum, tin, magnesium, iron, titanium, thorium, hafnium or rubidium.
Metal oxides of Group IVB metals are most preferred.
25 The anion bound to the metal oxide in the catalysts can ~9 ~ UD 13928 be inorganic anions and/or organic anlons. Inorganlc anlonic groups are preferred, wlth the sulfate group b~lng the most preferred.
Other anion-bound oxide catalysts can be used in place of anion-bound zlrconlum oxide catalyst, although the anlon-bound zlrconium oxide catalyst is most preferred. Examples of other anlon-bound metal oxides are anlon-bound lron oxlde (preferred), anion-bound alumlnum oxide, anlon-bound nickel oxide, anion-bound tln oxlde, anlon-bound magneslum oxlde, anion-bound rubldlum oxlde, anlon-bound titanlurn oxide (preferred), anlon-bound thorlum oxide (most preferred), and anlon-bound hafnlum oxlde (most preferred). Thorium oxide catalysts may be more advantageous than zirconium oxide catalysts since they are very lnsoluble and thorium is not amphoteric like zirconlum. Amphoteric means actlng as either an acid or base. Experimentation has found that anion-bound cerium oxlde, anion-bound ; lanthanum oxlde, anlon-bound tungsten oxide and certaln other anion-bound metals do not work as catalysts Ln the lnvention process of catalytlcally alkoxylat-lng certain compounds. This lack of catalytic activity of certain anion-bound metal oxldes shows the unexpected nature of the invention.
The metal oxldes used in the anlon-bound metal 283~9V~

oxlde catalysts are amorphous or used in amorphous form.
~or example, one uses the amorphous forms of alurnina as o~posed to the crystalline forms of alumina. The metal oxldes can also be primarlly or mainly amorphous, that isl more of the metal oxide is in the amorphous state than ln the crystalllne state. The crystalline formlng metal oxides, such as, calcium oxide, are not used.
Only solid, insoluble catalysts are used so that a hetero~eneous catalytic reaction is involved. Catalysts based on K, Ba and Na a~e soluble in the reactants and/or product and/or diluent, so they are not used in the lnvention.
1,4-dioxane or 1,4-diethylene dioxide is undeslrable, but is produced to a small extent by all of the lnvention catalysts. The anion in the catalyst needs to be bound totally or else it leaches into the reaction medium and increases the acidity with the resultant productlon of dioxane. Pre~erably 2 to 3 weight percent of the anion (e.g., SO4) is bound to the metal oxide. The use of Na2SO4 in place of H2SO4 elimlnates the minor dioxane p~oductlon caused by the latter, but Na2SO4 causes a slower reaction rate. In general, the more baslc the anion-bound metal oxide catalyst is, the less the amount of dioxane that is produced.

.. :

~2~33[)~3~

The anion-bound metal oxide catalyst is usually used in a flnely-dlvided particulate stake. Mixtures of a,nion-bound metal oxlde catalysts can be used.
Carriers or supports can be used to support the ani-on-bound metal oxide catalyst. The support is used in a partlculate form and can be porous or nonporous, although the former is prefer~ed. Usually the support particles have diameters between 1 and 5 mm.
Preferably, car~iers are used which are inert to the reactants and products of the sub~ect alkoxylatlon reactions.
The preferred carriers are sillca gel and 4 A
alumlna-silica sieves. Examples of other useful inert carriers are dlatomaceous earth, sllica, alumina (e.g., ~ - alumlna), slllca-alumina, calcined clays, charcoal and zeolltes.
The catalysts can even be used ln a porous, unsupported form.
The anlon-bound metal oxlde catalysts can be regenerated or reactlvated by calcination, for example.
Zirconium oxysulfate catalyst is preferably regenerated by calcination ln alr at a temperature of about 575C~
Generally regeneratlon calcination is run in air or oxygen at a temperature between 300 and 950Co ~
25 preferably between 500 and 800C., for a period of time ' ~2~33~9~

which is usually one to four hours, or more.
Generally the recovered catalyst does not have to b~ regenerated and can be used as is wlth no loss of selectivlty.
~ The reactants withln the scope of the invention are in the gaseous and/or liquld state, althou~h a reactant could be used ln the solid state lf lt was in a flnely-divided particulate form, for example, suspended ln A llquld carrler (dlluent) or a different llquld reactant. Solld reactants can also be used if they are ; dlssolved ln a liquid solvent. The anlon-bound metal oxlde catalyst ls used in a solld form.
Examples of liquid nonpolar dlluents from whlch the appropriate diluent can be selected are: acetlc acid nitrile, anthraceneJ benzene, chlorobenzene, 1,2-di-chlorobenzene, ethylbenzene, isopropylbenzene, l-lsopropyl-4-methylbenzene, nltrobenzene, propyl-benzene, 1~3J5 trlmethylbenzene, benzolc acid nitrlle, perchloro biphenyl, 1,3-butadlene, 2-methyl-1,3-butadlene, butane, butanoic acid nltrlle, carbondisulflde, carbon tetrachloride, chloroform, cyclohexane, methyl cyclohexane, perfluoro cyclohexane, ~; cyclopentane, decalln, decane, ethane, bromoethane, chloroethane, 1,2-dibromoethane, l,l-dichloroethane, difluoro-tetrachloro ethane, nltroethane, pentachloroethane, 1,1,2,2-tetrachloroethane, 1,1,2-trichloro ethane, trlchloro-trifluoro ethane, e~hylene, perchloroethylene, trichloroethene, heptane, perfluoroheptane, hexane, hexene-l, malonic acid dinitrile, methane, bromomethane, dichloromethane, dichloro-difluoro methane, cllchloromethane, nltromethane, tetrachloro-difluoro methane, trichloro-monofluoro methane, naphthalene, nonane, octane, pentane, l-bromopentane, 1-chloropentane, pentene-l, phenanthrene, propane, l-bromopropane, 2,2-dimethylpropane, 1-nltropropane, 2-nitropropane, propene, 2-methylpropane, propionic acid nitrile, styrene, hydrogenated terphenyl, tetralin toluene and m-xylene.
Examples of liquid moderately polar diluents from which the appropriate diluent can be selected are:
acetic acid butyl ester, acetic acid ethyl ester, acetic acid methyl ester, acetic acid pentyl ester, acetic acid propyl ester, N,N-diethyl acetic acid amide, N,N-dimethyl acetic acid amide, acrylic acid butyl ester, acrylic acid ethyl ester, acrylic acid methyl ester, adlpic acld dioctyl ester, benzoic acid ethyl ester, benzoic acid methyl ester, l-iodobutane, carbonic acld ester, vinyl chlGride, N,N~diethyl formic acid amide, N,N-dimethyl formic acid amide, formic acid ethyl ~L283~9;2 ester, formlc acid methyl ester, formlc acid 2-methylbutyl ester, formic acid propyl ester, furan, furfural, lactic acid butyl ester, lactic acid ethyl ester, methacrylic acld butyl ester, methacrylic acid ethyl ester, methacrylic acld methyl ester, oxalic acid diethyl ester, oxalic acid dimethyl ester, l-iodopentane, phosphoric acid triphenyl ester, phosphoric acid tri-2-toly ester, phthalic acid dibutyl ester, phthalic acid diethyl ester, phthallc acid dihexyl ester, phthalic acid dirnethyl ester, phthalic acid dl-2-methylnonyl ester, phthalic acid dioctyl ester, phthalic acid dipentyl ester, phthalic acid dipropyl ester, propionic acid ethyl ester, propionic acid ethyl ester, propionic acid methyl ester, l-methyl 2-pyrolldone, sebaclc acid dibutyl ester, sebacic acid dioctyl ester and stearic acid butyl ester.
Examples of liquid hydrogen-bonded diluents from which the appropriate diluent can be selected are:
N-ethyl formic acid amide, N-methyl formic acid amide 20 and N-methyl methacrylic acid amide.
Mixtures of inert diluents can be used.
The heterogeneous catalytic reactions of the invention can be effected, for example, in one of three ways: (1) ln batch processes; (2) in continuous 25 ~lxed-bed proce~ses; and (3) in continuous ~luldized :.

.

33~9Z

reactor processes. In a batch reactor, the catalyst is kept suspended ln the reactant by shaklng or stirring.
I~ a fluidized reactor, the catalyst ls at a particular original level. As the velocity of the reactant stream ls 1ncreased, the catalyst bed expands upward to a second level, and at a crltical velocity it enters into vlolent turbulence. The fluidlzed reactor is part1cularly useful for removlng or supplying the heat necessary to maintain a fixed catalyst temperature. The fluidized reactor can usually be employed only on a rather large scale slnce good fluidization requires a reactor larger than about 1.5 inch in diameter.
The process of the invention broadly involves the liquid or gaseous use of anion-bound metal oxide heterogeneous catalysts for the alkoxylation of actlve-hydrogen compounds, preferably hydroxyl-containing compounds, such as, primary or secondary alcohols~ diols or triols. Mixtures of active-hydrogen compounds can be used.
Active-hydrogen organic and inorganic compounds incIude, for example, hydrogen-containing compounds (ROH, polyols), carboxylic acids (RC02E3), thiols (RSH), amines (RNH2 or R2NH), ammonia, water, hydrohalic acids (HX where X is a halogen), alkyl-OCH2CH20H, HCN, and bisulfites of metals such as alkali and alkaline earth ~283~92 UD 13928 metals. R above is generally a saturated aliphatic hydrocarbon moiety ~branched or unbranched alkanes), a s~turated monocyclic moiety or an aromatic hydrocarbon moiety (l.e., an arene moiety). Such organic moleties ca~ be substltuted with nonreactive or non-lnte~ering 3ubstituents such as halogens, NO2, etc. The actlve-hydrogen compounds broadly have the formula HQ
(where Q 18 a saturated or aromatic organlc molety or an lnorganic molety).

The invention can be used to alkoxylate any of the primary or secondary monohydric alcohols, dihydric alcohols (dlols), trlhydric alcohols and polyhydric alcohols (polyols), glycol ethers and alkoxylated ethylene glycols, all o~ which are su~table active-hydrogen compounds provlded any particula~
lndivldual compound does not poison the anion-bound metal oxlde catalyst. Such hydroxyl-containing compounds can be substituted with non-interferlng groups, such as, nitro groups, halo groups and the llke.

The monohydric alcohols can be the primary alkyl (monohydrlc) alcohols having 1 to 12 carbon atoms, such as, methanol, ethanol, n-propanol, n-butanol, l-pent-anol, l-hexanol, l-heptanol, l-octanol, l-decanol, l-dodecanol, lsopropanol, lsobutanol, 2-methyl-1-25 butanol, 3-methyl-1-butanol, 2-methyl-1-pentanol, 3-~L283~2 methyl-l-pentanol, 4-methyl-1-pentanol, 2-ethyl-1-but-anol, and 2,4-dimethyl-1-pentanol. The monohydric ; a~cohols can be the secondary alkyl (monohydric) alcohols havlng 2 to 12 carbon atoms, such as, 2-buta-nolJ 2-pentanol, 3-methyl-2-butanol, 2-hexanol, 3-hex-anol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2,4-methyl-3-pentanol, and 2-octanol. The monohydric ; alcohols can be paraffinlc alcohols (the above alkyl-alcohols) or olefinlc alcohols (e~g~ allyl alcohol).
The monohydric alcohols can be alicyclic monohydric alcohols having 3 to 10 carbon atoms, such as, cyclo-hexanol, cycloheptanol, cyclopropanol, cyclobutanol, cyclopentanol and cyclooctanol.
The invention process can be used to alkyoxylate any of the allphatic, aromatic or heterocyclic compounds containing two hydroxy ~roups, preferably separated by at least two carbon atoms. The dlols can be substituted if desired with varlous noninterfer~ng (non-functional) substituents such as ether groups, sulphone groups, tertiary amlne g~oups, thioether g~oups, chlorine atoms, bromlne atoms, iodine atoms, fluorine atoms, etc.
Typical compounds which can be used a~e listed below merely by way of illustration and not lirnitation:
Ethylene glycol, diethylene glycol, 2,2-dimethyl propane-1,3 diol, butane-1,4-diol, hexane-1,6-diol, ~Z~3092 UD 13928 octane-1,8-dlol, decane-1,10-diol, dodecane-1,12-diol, butane-1,2-dlol, hexane-1,2-diol, l-0-methyl glycerol J
2~0-methyl glycerol~ cyclohexane-1,4-methyl-diol, hydroquinone, resorcinol, catechol, bis(parahydroxy-ph~nyl) butane, 4,4'-dihydroxybenzophenone, naptha-lene-1,5-diol, biphenyl-4-4'-dlol, 2,2-bls(3-methyl-4-hydroxyphenyl) propane, 2,2-bis(4-hydroxy-dibromo-phenyl) propane, etc.
Mixtures of different diols can be used. It is also withln the ~urview of the invention, though less - preferred, to use the compounds containing more than two hydroxy groups, for example, glycerol, diglycerol, hexanetriol, pentaerythrltol, etc. Moreover, it is within the scope of the inventlon to utillze the sulfur analogues o~ the dlols. Thus, for example, instead of using the compounds containing two hydroxy groups, one can use the analogues containing either (a) two -SH
groups or (b) one -SH group and one -OH group.
Among the pre~erred compounds are the aliphatic dlols, ~or example, those of the type:

HO (CH2)n wherein n has a value from 2 to 12. Another category of aliphatic hydroxyl-containlng compounds are the ~ :
..., ,,.. : ~.
~, .

polyethylene glycols, i.e.:

Ho_cH2_cH2- [0-CH2-CH2 ]~1-O-CH2-CH2-OH

wherein n has a value from zero to 10. A category of aromatic diols are the bisphenols, that is, compounds of the type:

Dl R~ ~ ~R' R OH
HO

wherein R-C-R represents an aliphatic hydrocarbon group contalnlng 1 to 12 carbon atoms and R' represents hydrogen or a lower alkyl radical, In this category are: 2,2-bis(parahydroxyphenyl) propane;
: 2,2-bis(3-isopropyl-4-hydroxyphenyl) propane; and bromlnated derivatlves of bisphenol A, such as, ~ 15 2,2-bis(4-hydroxy-dibromophenyl) propane~
; The alkoxylation of diols can p~ovide dimers or polymers.
The use~ul trihydric alcohols include glycerol, 1,2,3-butantriol and l,l,l-trihydroxymethylethane. The use~ul polyhydrlc alcohols include those having the formula CH2OH(CHOH)nCH2OH, wherein n is 2 to 5~ such as, ~2~331[)9Z

arabitol, adonltol, xylltol, mannitol and sorbitol.
Preferably the invention alkoxylation process is u~ed w$th glycol ethers, ethylene glycols (i.e., to produce CARBOWAX~-type products) or Tergltol-type products.
CARBOWAX~ ls the reglstered tradema~k o~ Unlon Carblde Corporatlon for a serles of polyethylene glycols. Ethylene glycol can be used to make the CARBOWAX~ polyethylene glycols or the CARBOWAX~
polyethylene glycols can be used to make higher molecular weight CARBOWAX~ polyethylene glcyols. For example, CARBOWAX~ polyethylene glycol 200 can be used to make CARBOWAX~ polyethylene glycol 400. Speclfically, the CARBOWAX~ polyethylene glycols are liquid and solld polymers of the general formula H(OCH2CH~)nOH, where n is greater than or equal to 4. In general, each CARBOWAX~ polyethylene glycol is followed by a number which corresponds to its average molecular weight.
Generally, the invention process is not prefe~red for using CARBOWAX~ polyethylene glycols having an average molecular weight above about 600 to 800 as startlng materlals because such CARBOWAX~ polyethylene glycols are solids at room temperature (although they are liquid at the reaction temperatures, e.g.z 110C.). Examples of useful CARBOWAX~ polyethylene glycols are: CARBOWAX0 ~83~

polyethylene glycol 200, whlch has an average n value of 4 and a molecular weight range of 190 to 210; CARBOWAX~
pplyethylene glycol 400, wh:Lch has an average n value between 8.2 and 9.1 and a molecular welght range of 380 to ,420; and CARBOWAX~ polyethylene glycol 600, which has an average n value between 12.5 and 13.9 and a molecular welght range of 570 to 630.
The anlon-bound zirconlum oxide catalyst has a high selectivlty to ethylene glycol. The reaction temperature ls not important and can be run at 50 to 110C at a 5:1 weight ratlo of H2O to ethylene oxide and at varlous catalyst concentratlons greater than 90 percent o~ ethylene glycol is produced. At a 10:1 weight ratio, greater than 95 percent of ethylene glycol is produced.

TERGITOL~ is the registered trademark of Union Carblde Corporation for a serles of the sodium salts of the acid sulfate of secondary alcohols of 10 to 20 carbon atoms which are nonionic or anionic su~factants.
Examples of the TERGITOL~ are: TERGITOL~ Pentrant 08, whlch is C4H9CH(C2H5)CH2SO4-Na; TERGITOL~ Pentrant 4, which is C4HgCH(C2H5)C2H4CH~(SO4Na)CH2CH( 3)2;
TERGITOL~ Pentrant 7, which is C4HgCH(C2H5)C2H4CH~

(so4Na)c2H4cH(c2H5)2 Examples o~ useful glycol ethers are ethylene 3~3Z

~lycol monoethyl ethe~, ethylene glycol monobenzyl ether, ethylene glycol monobutyl ether, ethylene glycol mpnomethyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol monooctyl ether, propylene glycol monomethyl ether and propylene glycol phenyl ether.
The actlve-hydrogen compound can be a saturated carboxylic acld, HOCOR. The carboxylic acid can be a stralght-chaln alkanoic acld (CnH2nO, wherein n is 1 to 35), such as, methanolc acld, ethanoic acid, propanoic acld, butanoic acid, pentanoic acld, hexanoic acid, heptanolc acld, octanoic acld, nonanoic acid, decanoic acld, undecanoic acid, dodecanoic acid, trldecanoic acid, tetradecanolc acld, pentadecanoic acid, hexadecanoic acid, heptadecanolc acld, octadecanolc acld, nonadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid, triacontanoic acid, trltriacontanoic acid, and pentatriacontarlolc acid. The active-hyd~o~en compound can be a b~anched alkanoic acid, such as, isopropanolc acid, lsobutanoic acid, 2-butanolc acid, 3-methyl-l-butanoic acid, 2-methyl-l-butanoic acid, 2-pentaonoic acid, 3-pentanoic acid~ 2-methyl-l-pentanoic acid, 3-methyl-1-pentanoic acid, 2-ethyl-l-butanoic acid, 2-hexanoic acid, 3-hexanoic ~za3~9~

acld, 2-methyl-2-pentanoic acld, 2,4-dlmethyl-3-pentanoic acid and 2-octanolc acid.
, The carboxyllc acld can be a dienoic acld (CnH2n 42)' such as, 2,4-pentadlenolc acid, 2,4-hexadlenoic acld, 2,4-decadienolc acld, 2,4-dodecadlenoic acld cls-9-, cis-12-octadecadlenolc acld, trans-9,trans-12-octadecadienoic acid, and 9,13-docosadlenoic acid~ The carboxylic acld can also be a trienolc acid (CnH2n_6O2), such as, 6,10,14-hexadecatrienolc acid, cis-9-, cis-12,cis 15-octadeca-trlenoic acid9 cls-9-, trans-ll,trans-13-octadecatri-enoic acld trans-9,trans-ll,trans-13-octadecatrienoic acld cis-9-, cis-ll,trans-13-octadecatrlenoic acid, and trans-9,trans-12,trans-15-octadecatrienolc acid. The carboxylic acld can further be a tetraneoic acid (CnH2n 82)~ such as, 4,8,12,15-octadecatetraenolc acid, 9,11,13,15-octadecatetraenoic acid, 9,11,13,15-octadeca-tetraenolc acld, and 5,8,11,14~eicosatetraenoic acid.
The carboxyllc acid can also be a pentaenolc acid (CnH2n 102)~ such as, 4,8,12,15,19-docosapentaenoic acid.
The carboxyllc acid can be a substltuted, saSurated carboxylic acid, such as, lodoacetic acid, o-nitrophenylacetic acid, p-nitrophenylacetic acid, trichloroacetlc acid, trifluoroacetic acid, bromoacetic .i :

3~

acld, 2-bromobutyric acid, 2-bromohexadecanoic acid, 2-bromohexanoic acid, 6-bromohexanoic acid, 2-bromo-3-~ethylbutyric acid, (p-bromophenoxy)acetic acid, 2-bromopropionlc acid, 3-bromopropionic acid, ll-bromoundecanoic acld, chloroacetlc acld, 3-chloro-buty^lc acld, 3-chloro-2,2-climethylpropionlc acid, (4-chloro-2-methylphenoxy)acetlc acid, o-chlorophenoxy-acetlc acld, p-chlorophenoxyacetic acld, 2-(o-chloro-phenoxy)p~oplonic acid, p-chlorophenylacetic acid, 2-chlorop~opionlc acld, 3-chloropropionic acld, 2,3-dlbromopropionic acid, dichloroacetic acid, 2,4-dichlorophenoxyacetic acid, (2~5-dihydroxyphenyl)-acetic acid, (3,4-dimethoxyphenyl)acetlc acid, 2,4-dinit~ophenylacetlc acld, (2,4-dl-tert.-pentyl-phenoxy)acetic acid, 2-(2,4-di-tert.-pentylphenoxy)-buty~ic acid, ethoxyacetic acld, 3~11-dihydroxytetra-decanoic acid, 2,15,16-trihydroxyhexadecanoic acld, aleoprollc acld and aleprestic acid. Normally, the substituents on any of the active-hydrogen compounds should be non-interfering, but if deslred, substituents having active hydrogens, such as, -OH or -SH, can be used (of course, not all -OH and -SH substituents will be reactive).
The actlve-hydrogen compounds can be a sulfonic acid, RSO3H, wherein R is a univalent organic radical ' ' ` ' ` ' ' ... r.. ,.. . :.. ,.~, . . . .

1~8309~

tsaturated, alicycllc o~ aromatic) J such as, the alkanesul~onic acids~ for example, methanesulfonic acid, e,thanesulfonic acid, propanesulfonic acid, butanesul~onlc acid, pentanesulfonic acid and he~anesulfonic acld, alkarenesulfonic acids (RnARS03H, where R is alkyl and n is l to 3), such as, p-toluenesulfonic acid, arenesulfonic acids, such as, 2-naphthalenesul~onic acid, l,3-benzenedlsulfonlc acid, 2,6-naphthalenedis~llfonic acld and 1,3,6,8~naphthalene-tet~asul~onic acid, fluorlnated and chlorofluorinatedsulfonic acids, such as, CF3S03H, ClCF2S03H, Cl2C~S03H~
CHF2S03H and ClCHFS03H, other substituted sul~onic aclds, such as, p-hydroxybenzene sulfonlc acid, and other sulfonlc acids, such as, methanedisul~onlc acld and methanetrlsul~onlc acld.
The active-hydrogen compounds can be other sul~ur aclds where sulfur is substltuted for one or more oxygens in the carboxylic group, such as, methanethlollc acid (HCOSH), methanethionlc acid (HCSOH), ethanethionic acid (CH3COSH), ethanethlonic acid (CH3CSOH), methanethionothiolic acid (HCSSH) and ethanethiono-` thiollc acid (CH3CSSH).
The active-hydrogen compounds can be alkanethiols (e.g., having 1 to 20 carbon atoms), such as, methanethiol, ethanethiol, 2-propanethiol, ~2~33~9~2 l-propanethiol, 2-methyl-2-propanethiol, 2-butanethiol, 2-methyl-1-propanethiol, l-butanethiol, 1-pentanethiol, l,-hexanethiol, l-heptanethlol, l-octanethiol, l-decanethiolJ 1 dodecanethiol, l-hexadecanethiol, l-octadecanethiol, and cyclohexanethiol, and aromatic thiols, ~uch as, benzene thiol (or phene thiol).
Besides monothiols, other thiols can be used such as dithiols, trithiols and tetrathiols (e.g., 1,2-ethanedithiol), and substituted thiols (e.g., l-amino-2-propane thiol).
Thioglycolic acid and other sulfur analogue acids can be used as the active-hydrogen compound.
The active-hydrogen compounds can be alkyl-OCH2CH20H, such as, Cellosolve~ (C2H50CH2CH20H), methyl Cellosolve~ and butyl Cellosolve~.

The active-hydrogen compounds can be bisulfites of metals, such as, NaHS03, KHS03, LiHS03, Mg(HS03)~, Zn(HS03)2 and Be(HS03)2.
The alkoxylating compounds used in the invention alkoxylation process are epoxide compounds having the !, formula:

.
~0~ 1 RlR2C ~--- 3 4 . ~ .

. , .

~ Z !33~Z

~herein Rl, R2~ R3 and RL~ are each H or -(CH2)nCH3, and whereln n is 0 to 3, with the proviso that Rl, R2, R3 and-R4 can be the same or different. The useful epoxldes are basically derivatives of ethylene oxide.
Examples of the alkoxylating compound are ethylene oxide, propylene oxide, trimethylene oxide (2-methyloxlrane), isobutylene oxide, 2,2,3-trimethyloxirane, cis-2-butene oxide, trans-2-butene oxide, ~ -butylene oxide, 2,2,3,3,-tetramethyloxirane, 2,3-diethyleneoxirane, 2,3-dipropyleneoxirane, 2,3-dibutyleneoxlrane, 2-butyleneoxirane, 2-isobutyleneoxirane and 2-ethylene-3-propylene oxirane. The preferred alkoxylatlng agent is ethylene oxide because lt is much more reactive than propylene oxide and the higher members of the subJect epoxide compounds.
A narrow molecular weight range of products is produced with a minimum of undesirable high molecular weight by-products or co-products.
The following examples are illustrative of the invention.
.

.

q.z~3~09Z

P,reparation 0~ Sulfate~Bound Zirconium Oxide Catalyst 500 ml. of NH40H (14.8M), 500 ml. of distilled water and 64.5 g of zlrconyl chloride (yellow solld) were combined and the mixture was placed in a 2 liter beaker having a watchglass cover. The solution was stirred for 3 hours. A ~ine white solid rormed quickly as the stir~lng began. The llquid was filte~ed off in a Buchner ~unnel. The solid filtrate was placed in a vacuum oven and dried at 100C. and 30 inches of ~acuum.
After drying in the vacuum oven, about 35 g o~ white solid was obtained. The solid was washed in a Buchner funnel using a total of 25 ml. o~ water. The solid was then treated with lN H2S04 in the form of an acidlc aqueous solution (pH 1). The solid was divided and placed in two Pyrex tubes. The solid was calcined ~or 3 hours at 600C. (with air flow). The calcined solid was light yellow and was sulfate-bound zirconium oxide (catalyst). 29.6 g of the catalyst was obtained. The pH of the catalyst in water was acidic.

~283~92 ~D 13928 Preparation Of CARBOWAX~ Polyethylene Glycol 200 Using Sulfate-Bound Zirconlum Oxide Catalyst 50.7 g of ethylene glycol and 5.0 g of sulfate-bound zirconium oxide catalyst (prepared by the method of Example 1) were charged to a Parr bomb. The bomb, three tlmes, was purged with N2 and evacuated. The bomb was left under 15 pounds per square inch gauge of pressure of N2. The bomb was heated and stirred vigorouslyO Ethylene oxide was added to the bomb based on the following schedule:

;~ TABLE I

; Reactor Reactor Total Ethylene Time, Temp. 3 Pressure, Oxide Feed, 15 Mins. C. p~Soi~g~ 1grams 0 8L~ 18/41 6.o ~ 96 24/36 8.1 - 7 86 24/40 13.2 81 24/36 16.1 ;~ 20 14 79 24/36 19.8 ~Z83~

17 81 24/40 25.7 23 78 24/42 32.1 ,31 820 24/39 37.1 79 24/37 40.6 48~ 81 26/43 ~6.2 59 840 27/45 52.2 73 820 29/44 57.6 81 30/41 61.1 163 840 29/45 67.2 10212 84 30/45 71,9 234 104 33/54 75.3 241 93 34/56 80.2 307 97 38/60 94.2 15322 98 41/63 99~ 6 349 97 42/65 105.1 355 96 57/65 106.9 37 97 52/68 110.8 375 97 62/6~ 112.8 Note:
1. The first number is~ the p~essure be~ore the .

8 3~ UD 13928 ethylene oxide addition, and the second number is the pressure after the ethylene oxide addition.

An exotherm of 8 to 9 CO occurred immediately aftSr the ethylene oxide was added to the bomb. The pressure began to quickly drop. Further exotherms of 8 to 9C. occurred after each addition of ethylene oxide through the addition totalling 40.6 grams. Then no exotherm was observed in con~unct~on with ethylene oxlde additions until the addition totalling 67.2 grams. At that an exotherm of 4 to 5C occurred. Even larger exotherms occurred thereafter at some of the subsequent ethylene oxide additions. The temperature was raised to 100C. before the addition totalling 75.3 grams. The pressure dropped back quickly and completely after ethylene oxide additions during the first part of the run, but slowed somewhat later in the run. (The pressure dropped faster after reaching 28 p.s.i.g.) Presure also began building later in the run, but this was partly a function of the increased temperatureO
(The pressure rose from 31 p.s.i.g. to 33 p.s.i.g. when the temperature was raised to 100C.) After 600 minutes the heat was shut off from the bomb. The product was slightly hazy (possibly due to fine catalyst particles in suspension therein), had a pH of 7 and was slightly -gL2y33o~z viscous. The product was analyzed uslng vapor phase chroma~ography. The product was CARBOWAX~ polyethylene g,lycol 200 produced by the ethoxylation o~ ethylene glycol~
The sulfate-bound zirconium oxlde catalyst was recovered usine a flne sintered glass funnel. The recovered catalyst was washed with ethylene glycol - the pH at thls point of the catalyst in water was neutral.
The catalyst was then washed wlth methyl alcohol - the pH was neutral. The catalyst was dried ln an oven at 130C.; after 1.5 hours the pH of the catalyst was 3;
and after 3 hours the pH of the catalyst was 3. The recovered catalyst was then calclned for 1.5 hours at 575C. with an airflow.

_.

Preparation of Methyl Cellosolve~ Using Sulfate-Bound Zirconlum Oxlde Catalyst 50.0 g (1.56 moles) o~ methanol, contalnlng 0.225 percent of water, and 1.0 g o~ sulfate-bound zirconlum oxlde catalyst (prepared by the method of Example 1) were charged to a Parr bomb. The bomb was purged with N2 and evacuated three tlmes. The bomb was left under 16 p.s.i.g. of N2. The bomb was heated and stlrred ",. , ~ . ~

~33C)~Z

vigorously. Ethylene oxlde was added to the bomb based on the following schedule:

, TABLE II

Reactor Reactor Total Ethylene 5Tlme, Temp., Pressure, Oxide Feed, Mins. C. p.s.l.g. grams 0 81 34/:38 3.5 19 79 35/35 7.1 7o 790 36/46 12.0 10123 79 40/47 17.2 overnite 16 20 It took 7 mlnutes for the pressure to reach 36 p.s.i.g.
in the bomb, at which tlme the ~irst addition was made.
The pressure reached 36 p.s.l.g. at the 45 mlnute point.
The reactants reacted at the moderate rate, i.eO, "cooked down'l well. After 179 minutes the heat was shut o~f from the bomb. The product was methyl Cellosolve~

produced by the ethoxylation of 20 methanol.

.. ; ~ . : , . . .
:;

~D 13928 42 1~ a3092 Example 3 was repeated, except that the sta~ting methanol contalned 0.768 percent o~ water (water was a~ded). The reaction occurred at about the same rate as in Example 3, but the reaction "cooked down" to slightly lower pressure. The product was methyl Cellosolve~
p~oduced by the ethoxylation of methanol.

~ xample 3 was repeated, except that the starting methanol contained 0.0315 percent water. The methanol was dried over actlvated ~ A sieves. The reaction occurred at about the same rate as and "cooked down"
slmilarly to Example 3. The product was methyl Cellosolve~ produced by the ethoxylation of methanol.
All of the above water determinations ln Examples 3 ~ to 5 were made on a Photovolt Aquatest IV electronic `' 10 titratOr.
The purpose of Examples 3 to 5 was to determine the effect of water content on the preparation of methyl Cellosolve~ using sulfate-bound zirconium oxide catalyst. The reactions in Examples 3 to 5 we~e run with all of the conditions the same except for the water content of the starting alcohol. Water did not seem to adversely effect the reaction rate, in fact, a slight increase ln activity was observed. The conversion to product could not be correlated with the water content.
A peak was observed in all of the vapor phase chromatography scans with retentlon time similar to ethylene glycol, but the area percent of this peak did not vary significantly between runs.

Preparation Of CARBOWAX~ Polyethylene Glycol Using Sulfate-Bound Zirconium Oxide Catalyst 52.9 g of ethylene glycol and 5.0 g of sulfate-bound zl~conium oxide catalyst was charged to a Parr bomb. The bomb was purged with N2 and evacuated three tlmes. The bomb was left under 16 p.s.i.g. of N2. The bomb was heated to 80C. and stirred vigorously.
Ethylene oxide was added to the bomb based on the following schedule:

TABLE III

Reactor Reactor Total Ethylene Time, Temp., Pressure, Oxide Feed, Mins. C. p.s.i.g~ grams :
15 0 7O 19/40 6.3 6 77 20/40 12.4 12 77 22/44 19.4 21 82 23/44 26.4 77 24/43 33.4 2045 81 26/46 41.1 .:. ~

~L~B'30~92J

48 80 2~

An exotherm of about 30C. occurred upon the first addltion of ethylene oxlde. The ethylene oxide was rapidly consumed. The exothe~ms became smaller on subsequent additlons. At the slx minute addition, the ; exotherm went to 99C. At the 30 minute addition, the exotherm went to 84C. At the 45 mlnute add~tion, the exotherm went to 85C. The rate of ethylene oxide consumptlon also decreased, and the pressure built up somewhat in the bomb (posslbly due to volume effect).

After 48 minutes the heat was turned off and the catalyst was flltered off from the liquid p~oduct. The product was analyzed using vapor phase chromatography.
The sample tested contained 0.21 percent of dioxane.
The product was clear and colorless and had a neutral pH. The product was CARBOWAX~ polyethylene glycol (viscous liquld polyethylene glycol) prepared by the ethoxylatlon of ethylene glycol.

3~Z

' J
Preparatlon of CARBOWAX~ Polyethylene Glycol Using ; Sulfate-Bound Zlrconlum Oxide Catalyst The flltered sulfate-bc)und zi~conium oxide catalyst (5.0 g) from Example 6 was placed ln a Pa~r bomb. The catalyst was not washed, so a small amount of the liquid product of Example 6 remained in the bomb. 50.7 g of ethylene glycol was charged to the bomb. The bomb was pu~ged with N2 and evacuated three timesa The bomb was left unde~ 16 poS~i~g~ of N2. The bomb was heated and stl~red vigorously. Ethylene oxide was added to the bomb based on the following schedule.

TABLE IV

Time, Reactor Reactor Total Ethylene 15 mins. Temp~, P~essu~e, Oxlde Feed, C. p.s.i.g. grams 0 81 19/37 6.2 9 79 22/42 11.9 17 77 24/39 16.5 1 Z83~92 An exotherm to 90C. occurred upon the first addition of ethylene oxide. The exotherm was not as great as and the rate of reaction was slower than the lnitial reaction in Example 6. At the 9 minute addition, the exotherm went to 880C. At the 17 minute addition, the exotherm went to 86C. The catalyst apparently lost some actlvity during the reaction. After 27 minutes the heat was turned off and the bomb was allowed to set at room temperature for about 64 hours. The product was analyzed using vapor phase chromatography. The sample tested contained 0.29 percent of dioxane. The product was clear and colorless, and had a neutral pH. The product was CARBOWAX~ polyethylene glycol prepared by the ethoxylation of ethylene glycol.

.~
Preparation of CARBOWAX~ Polyethylene Glycol ~sing ; Sulfate-Bound Zirconium Oxlde Catalyst 42.3 g. of ethylene glycol and 4.2 g o~ sulfate-bound zirconium oxide catalyst were charged to a Parr bomb. The bomb was purged with N2 and evacuated three times. The bomb was left under 16 p.s.i.g. o~ N2. The 30~Z~

bomb was heated and stirred vigorously. Ethylene oxide was charged to the bomb based on the following schedule:

TABLE V

Time, Reactor Reactor Total Ethylene mlns. Temp., Pressure, Oxlde Feed~
C. p.s.i.g. grams 0 820 18/41 6.4 9 77 20/41 12.3 21 80 22/46 18.8 An exotherm went to 99C. upon the first addition o~ the ethylene oxide. The ethylene oxide was consumed fairly ~ rapidly. The second additlon of ethylene oxide produced ; only a small exotherm (to 84C~) and the reaction slowed ; considerably. At the 21 minute additlon, the exotherm went to 82C. The product was analyzed using vapor phase chromatography, indlcattng that a substantial amount of product was produced. The sample contained 0.12 percent of dioxane. The product was colorless and sllghtly hazy (probably due to catalyst in suspension).
The product was CARBOWAX~ polyethylene glycol prepared ~2 830g ~ UD 13928 by the ethoxylation of ethylene glycol.

Hydrolysis Of Zirconyl Chloride 500 ml. of dlstilled wat;er and 64.5 e of ZrOC12.8H20 were placed ln a beaker and mixed. 40 ml.
of concentrated NH40H solution was added with mixlng to the beaker. The pH of the mixture was about 10. 8.4 ml. of concentrated HCl solution was added to the admixture to bring the pH back to 7. The admixture was filtered on a M sintered glass funnel. The pH of the solid filtrate in water was neutralO The solid filtrate was placed in a large Soxhlet extractor mounted on a 2 liter flask. The solid filtrate was washed with distilled water in the Soxhlet extractor. The liquid mixture was refluxed in the Soxhlet extractor for 13.5 hours. A check of the solid for Cl was essentially negative. The solld was dried overnight in a vacuum oven at 100 to 110C. and 30 inches of vacuum over MgS04. The solid was slightly off white and had the consistency of talcum powder tvery fine). The solid was not a hard cake as had been previously observed in thls example. 28.09 g of the solid were recovered - the ~3~ UD 13928 solid had a neutral pH in water. The solid was placed in 400 ml. of distilled water. Stirring was started and the pH was 7. After stlrring for 2 hours the pH was still neutral. The llquid admixture was filtered on a C
sintered glass funnel. Some of the solid passed through thé filter. The solid ~iltrate was placed in a vacuum oven at 80~C. and at 30 inches of vacuum over MgSO4.
The flltrate was dried over a weekend in the vacuum oven (the temperature reached 90C.). The solid was slightly A 10 off-white in color and was a fine free-flowing powder.
The pH of the solid in water was neutral; this was the first tlme the pH indicated neutral for Zr(OH)4. The product was zirconium hydroxide.

15 Preparation of Various Anion-Bound Zirconium Oxide Catalysts Four samples of Zr(OH)4 (prepared by the method of Example 10) were each treated with a dlfferent solution, respectively, of NH4BF4, (NH4)2HPO4, (Me4N)PF6 and 20 H2SO4. (Me4N)PF6 is tetramethylammoniumhexa~luorophos-phate. NH4BF4 is ammonium tetrafluroborate. Reference is made to Table VI below ~or the treating agents and ~.q~3~2 other presslng data. Each Zr(OH)4 sample in the respective solution was stirred for 5 to 10 minutes and ~hen filtered on a Buchner funnel. Each of the four solids was calcined in a Pyrex tube at 575C. (w1th an air flow) for 3 hours.

33C)~

o el qo ~l ~o3~

'3 o, ~'~83~92 5 g of the calcined filtrate from the sulfuric acld treated material was washed overnight with distilled w~ter in a Soxhlet extractor. The distilled water a~ter the wash had a pH of 2 to 3 and had a very fine, white, gel~tinous solld floating in it. The wash water tested positive for SO4(BaC12 test). The solid was removed from the Soxhlet extractor. The solid in water had a pH
of 4. The solld was then calcined in a Pyrex tube at 575C. (with an air flow) for 3.5 hours. After calcinlng the solid was yellow; upon cooling, the solid turned light yellow. The solid product in water had a pH of 2. The product was sulfate-bound zirconium oxide catalyst.

-Preparation Of CARBOWAX~ Polyethylene Glycol Using Phosphate-Bound Zlrconium Oxlde Catalyst 42.9 g of ethylene glycol and 4.17 g of zirconium oxy acid phosphate catalyst (as prepared in Example 10) were charged to a Parr bomb. The bomb was purged with ; 20 N2 and evacuated three times. The bomb was left under 16 p.s.l.g. of N2. The bomb was heated and stirred vigorously. Ethylene oxide was charged to the bomb based on the followlng :chedule:

. . .

, ` ~ ~
~LZ~330~2 ,~S ~ ~ S~

o C o = o ~ cn ct~

r ~ ~ r~ r S

O o o o ~ O o. ~ C

r~ r ,~ `r ~

-Upon flrst addlng ethylene oxide, a 30C. exotherm occurred. Thereafter, the exotherms decreased. Also, t,he rate of reaction, which was very rapld at flrst, slowed as the reaction proceeded. Durlng the run, the re~ction was stopped after 23 minutes and later started up again by contlnued heatlng and further ethylene oxlde additions. The liquid product was analyzed using vapor phase chromatography. The product contained 0.25 percent of dioxane. The product was clear and pinkish and was a little hazy (probably due to catalyst ln suspension). The pinkish color was due to a bad batch of ethylene oxide, which had a slight color and fine particulates ln lt. The pH of the product was neutral.
The catalyst was filtered off from the liquid product.
At that point the pH of the catalyst was 1 to 2. After washing the catalyst with methanol, the sllghtly wet catalyst (from methanol) had a pH of 3. The product was CARBOWAX~ polyethylene glycol prepared by the ethoxylation of ethylene glycol.

" ' ,' ~a30'9Z
~D 13928 Ethoxylation Of l-Butanol Uslng Sulfate-Bound Zirconium Oxi~e Catalyst , 57,9 g of l-butanol and 4.96 g of sulfate~bound zlrconlum oxlde catalyst (as prepared ln Example 10) were charged to a Parr bomb. The pH of the mlxtu~e was neutral. The bomb was purged with N2 and evacuated three times. The bomb was left under 17 p.s.l.g. of N2.
The bomb was heated and stlrred vlgorously. Ethylene oxlde was charged to the bomb based on the following ~chedule:

"'.' 3q~3~X

I Yl 1~ . ~ e~~ ~7~a I:E' ~

~1 ~ ~ .
~1 ~

o~ ~ r~
=

~, ~1 o~ o~ Z

~,'28309~

Upon flrst adding ethylene oxide, a 22C. exotherm occurred with rapid reaction of the lngredients. The s~econd ethylene oxide produced a rnuch smaller exotherm and the reaction rate was slower. The temperature was ral~sed to about 100C~, whereupon the rate of reaction was faster and the exotherms lncreased for awhlle.
After 73 minutes, the heat was shut off and the sealed bomb was allowed to set overnight. Two more additlons of ethylene oxlde were made. The bomb was evacuated before the sample was taken in order to remove excess ethylene oxlde. The product was analyzed uslng vapor phase chromatography and shown to be ethoxylates of l-butanol. It was difficult to determine that dloxane was produced due to the close proximlty of dioxane retentlon time to that of l-butanol. The ll~uld product was fairly clear, and had a sllgh~ color due to catalyst in suspenslon and from the bad batch of ethylene oxlde.
The pH of the product was neutral.

:`

~83~ UD 13928 J

Hydrolysis of Zirconyl Chloride and Treatment With Su~furic Acid 16 g of ZrOC12 8H20 was dissolved in 200 ml. of ; 5 dlstllled water 1n a 500 ml. Erlenmeyer flask. 21 g of silica gel and 50 ml. of water (to aid stlrring) were added. Enough NH40H was added while stirrlng to obtain a pH of 7. The mixture became very thlck as a white gelatinous precipitate formed. The solution was stirred for about one hour. A solid was filtered out and dried overnight in a vacuum oven at 80 to 90C. and under 30 lnches of vacuum over MgS04. 29.33 g of sillca gel and a flne whlte solid was recovered. The material had a pH
ln water of 3. The material was sieved on a U.S. No. 8 screen to ellminate the fines - 22.10 g of greater than 8 mesh material remained. The sillca gel appeared to be coated with white material. The silica gel fizzed and broke up when placed in water. 22.10 g of the silica gel was treated with 166 ml. of lN H2SO4 and then 2n calcined in Pyrex tubes at 575C. (with alr flow) for 3 hours. The material appeared physically unchanged and still had a "coated" appearance. The pH of the material ~.Z83~9~ , in water was 2 to 3. 20.2 g of the product was obtained. The solid product was sulfate-bound zlrconium o~ide catalyst bound to silica gel carrier.

.
, EXAMPLE 14 Hydrolysls Of Zirconyl Chloride And Treatment With Sulfuric Acid 16 g of ZrOC12 8H2O was dissolved in 200 ml. of distilled water in a 500 ml. Erlenmeyer flask. 41 g of 4 A sieves and 100 ml. of water (to aid stirring) were added. Enough NH40H was added while stirring to obtaln a pH of 7. The mixture became very thick as a white gelatinous precipltate formed. The solution was stirred for about one hour. A solid was filtered out and dried overnight in a vacuum oven at 80 to 90 C. and under 30 inches of vacuum over MgS04. The material had a neutral pH in water. The materlal was sieved on a U.S. No. 20 screen to eliminate the fines - 49.49 g of the greater than 20 mesh material remained. The sieves appeared to have abso~bed Zr(OH)4, a white powder - very little fines were present~ The sieves appeared to have white powder on their surface, but the color was uneven. 10 g. of the sieve mater~al was treated with 75 ml of lN

. :

3~ ~

H2S04. Some white color went into the H2S04. The H2S04-treated sieve material was calcined in Pyrex tubes ~t 575C. (with air flow) for 3 hours. Some f~ne particles were present after calcining. The pH of the sleve material in water was 5 to 6. The solid product was sulfate-bound zirconium oxlde catalyst bound to 4 A
sieves.

Preparation Of CARBOWAX~ Polyethylene Glycol Using Sillca Gel-Supported Sulfate-Bound Zlrconlum Oxide Catalyst 155.2 g of ethylene glycol (a syrupy liquld) and 20.2 g of silica gel-supported sulfate-bound zirconium oxide catalyst (as prepared ln Example 13) were thoroughly mixed and placed ln the reactor tube (one inch diameter) of a recirculatlng loop reactor. The reactor tube was purged with N2 and evacuated three times. The reactor tube was left under 15 p.s.i.g. of N2. The reactor tube was heated to about 80C.
Ethylene oxide was charged to the reactor tube based on the following schedule:

~ ~83~9h Reactor Reactor Total Ethylene Time, Temp.,l Pressure, Oxide Feed, Mins. C. p.s.i.g. grams 0 800/820 19/32 5.1 780/970 22/40 8.1 9 75/98 22/40 10.7 13 70/820 22/42 12.1 18 800/780 22/42 13.4 22 75'/73 22/43 14.7 26 780/740 22/45 16.2 31 79/73 22/45 17.4 36 72/70 22/45 18.7 41 77/68 22/45 20.1 46 80o/68 22/42 2105 52 850/670 22/52 24.2 57 76/72 24/52 29.7 63 80/79 24/56 35.6 79 780/760 24/55 43.3 84 80/69 23/55 50.9 92 790/69 24t54 58.6 102 83/760 26/55 65.5 116 83/71 26/55 72.1 127 80/700 25/55 80.3 142 (2) 81/69 28 ~2~

174 850/600 28/58 85.1 195 830/670 30/58 90.0 199 85/64 30 91.9 Note: 1. The first number ic; the temperature of the bomb, and the second number is the temperature inslde of the reactor tube.

2. Reactor shut down overnight and then restarted.

To samples taken durlng the run and the final product were analyzed by means of vapor phase chromatography.
The product had a pH in water of neutral. The catalyst was washed with methanol to remove color caused by ethylene oxide. The product was CARBOWAX~ polyethylene glycol produced by ethoxylation of ethylene glycol.

Preparation Of Sulfate Bound Zirconium Oxide Catalyst lO g of Zr(OH)~ and 150 ml. of 0.5N H2S04 were placed in a beaker and stirred for a few minutes. The solld was flltered off from the solution. The solid was calcined in a Pyrex tube at 575C. (with air flow) for 3 3/4 hoursO The calcined solid was white and had a pH
ln water of 1. The solid was stored in a desiccator unt-il needed. The product was sulfate-bound zirconium oxlde catalyst.

Ethoxylation Of 2-Octanol Using Sulfate-Bound Zirconlum Oxlde Catalyst 49.9 g of 2-octanol and 3.0 g of sulfate~bound zlrconium oxyide catalyst (as prepared by the method of Example 16) were charged to a Parr bomb. The bomb was purged with N2 and evacuated three times. The bomb was left under 15 p.s.i.g. of N2. The bomb was heated and stlrred vigorously. Ethylene oxide was added to the bomb based on the following schedule:

~283~9~

TABLE X

Reactor Reactor Total Ethylene Time, temp., Pressure, Oxlde Feed, Mins. C. p.s.l.g. grams .

0 82 18/366.6 7 (1) 30 11 115 31/5411.4 19 112 31/5817.0 44 108 33/5220.2 52 107 48/4920.5 113 107 26 20.5 Note: 1. The reactor temperature was lncreased to 110C.

Immedlately after the ethylene oxide was added to the bomb an exotherm to 85C. occurred. At the 7 minute polnt ln the run, the temperature of the reactor was increased to 110C. and the reactor pressure ~ose to 31 p.s.i.g. When ethylene oxide was added at the 11 mlnute point in the run, an exotherm to 125C. occurred. No noticeable exotherms occurred thereafter during the run.
The product was analyzed using vapor phase chromatography. The product had a neutral pH in water.

~28309~ UD 13928 The product ~as ethoxylates of 2-octanol.
;

, EXAMPLE 18 Pre~aration Of Sulfate-Bound Zirconium Oxide 50 g of commercial Zr(OH)4 (sllghtly damp, file white powder, with NH3 odor) was washed free of NH3 with distilled H2O. After the 750 ml. washing, the pH was neutral. The powder was washed with an additional 250 ml. of dlstllled H2O. The pH was still neutral. A

check of the wash water for Cl was negative (AgNO3 test). The powder was dried overnight in oven at 100C.
in an open beaker. 29.61 g of fine white powder was - removed after drylng. No NH3 odor was evident. The pH
of the solid in H2O was neutral.
10 grams of the treated Zr(OH)4 was treated with 150 ml. of lNH2S04 in a beaker with stirring for 5 to 10 minutes. The solution was filtered on No. 42 filter paper. The solld filtrate was dried for 2.5 hours in an open beaker in a 100C. oven. The pH of the filtrate in wate~ waq 3. The solld was calclned in a Pyrex tube at 575C. (with air flow) for 2-3/4 hours. The pH of the ~; calcined solid ln water was 0 to 1. One liter of distilled water and the solid were stirred overnight in ~' .
.

~33C~

a beaker at room temperature. The slid was ~iltered off. The solid filtrate was calcined in a Pyrex tube at 5~75C. (with air flow) for 3.5 ours. The calcined solid was white and had a pH in water of l to 2. The product was sulfate-bound zlrconium oxlde catalyst.

Preparatlon Of Phosphate-Bound Zlrconium Oxide Catalyst 10 grams of the treated Zr(OH)4 (prepared by the method of Example 18) was treated wlth 150 ml. of lN
(NH4)2HPO4 solutlon ln a beaker with stlrring for 5 to 10 minutes. The solutlon was filtered on No. 42 filter paper. The solid filtrate was dried for 2.5 hours in an open beaker in a 100C. oven. The pH of the flltrate in water was 8. The solid was calcined in a Pyrex tube at 57-5C. (with air flow) for 2-3/4 hours. The pH of the calcined solid in water was 2. One liter of distilled water and the solid were stirred overnight in a beaker at room temperature. The solid was filtered off. The solid flltrate was calcined in a No. 5 Pyrex tube at 575C. (with air flow) for 3.5 hours. The calcined solld was llght yellow and had a pH in water of 3 to 4.
The ~irconlum oxy-anlon product was phosphate-bound . . .

~~3092 zirconlum oxide catalyst.

~ EXAMPLE 20 Pr~paration Of Fluoride-Bouncl Zi^conlum Oxide Catalyst 9.61 grams of the treated Zr(OH)4 was treated with 150 ml. of lN HF solution in a beaker with stlrring for 5 to 10 minutes. The solution was filtered on No. 42 fllter paper. The solid filtrate was dried for 2.5 hours ln an open beaker in a 100C. oven. The pH of the ~iltrate in water was 4. The solid was calcined in a ; 10 Pyrex tube at 575C. (with air flow) for 2-3/4 hours.
One liter of distilled water and the solid were stirred overnlght in a beaker at room temperature. The solld was filtered off. The solid filtrate was calcined in a Pyrex tube at 575C. (with air flow) for 3.5 hours. The calcined solid was pinkish and had a pH in water of 4, and was stored in a desiccator until needed. The produc~ was fluoride-bound zirconium oxide catalyst.

~.

33C~

J

Preparation Of CARBOWAX 200~ Polyethylene Glycol Using Phosphate-Bound Zlrconium Oxide Catalyst 51.3 g of ethylene glycol and 5.0 g of phosphate-bound zlrconlum oxlde catalyst (p~epared by the method of Example 19) were charged to a Parr bomb.
The pH of the mixture was 5. (The pH of ethylene glycol by itself was 6.) The following formula was used to determine the amount of ethylene oxide needed:

Wt. Of Starting Compound x M.W. of Product Wt. Of Starting Compound Wt. of Product - Wt. Of Starting Compound Wt. Of Ethylene Oxide 51.30 g x 200 165.30 g (Product) - 51.30 g 62.07 g Y

Y = 114.0 g of Ethylene Oxide The bomb was purged wlth N2 and evacuated three times.
The bomb was left under 16 p.s.i.g. of N2. The bomb was heated to 80C. and stirred vigorously. Ethylene oxide was charged to the bomb based on the following schedule:

` ` ~æ~3~9-~:

TABLE XI
Reactor Reactor Total Ethylene Time, Temp.,Pressure, Feed, Mins. C.p.s.i.g. Grams - 0 77 19/28 3~
79 23/38 8.2 8 88 32/45 12.2 9 91 40/47 14.3 91 40/47 16.1 12 89O 40/47 18.1 14 860 40/46 19.6 16 820 40/46 21.7 17 78 40/46 23.5 83 40/46 24.9 23 82 40/46 26.8 78 40/46 28.1 28 830 40 40.1(3) 59 83 43 (3) 59 81 26/44 46.1 61 83 40/50 50.0(3) 76 (2) 44 81 126 40/57 51.9 84 130 40 (3) 246 122 54 97.0 314 122 51/56 97.8 30~

324 121 51/58 9~.7 338 121 51/64 99.7 356 122 52 100.8 364 122 52/72 102.4 , 378 122 54/72 103.7 394 121 54/72 104.6 414 122 54/72 107.0 438 122 54/64 105.0 439 121 55/76 109.4 454 121 56/74 112.3 484 121 56/80 114.7 50~ 121 60 (4) 17 38 ; Note: 1. Turned off reactor heat and restarted the next day.
.

2. The reactor temperature was increased to 125C.

3~ Constant feed o~ ethylene oxide to the the reactor and then the periodic addition was resumed as indicated.

4. The reaction heat was Cllt and the -- ~z~9~ ~

ingredlents were allowed to set ove~nlght in the sealed bomb.

The reaction proceeded rapidly and an exotherm of 4 to 10C. was observed on the first few additlons. The rate Or reaction slowed somewhat as ethylene oxide was added, but still was fairly rapld; and pressure built up somewhat (some due to volume effect). The bomb was allowed to set overnight at room temperature after 40.1 g of ethylene oxide had been added. The reaction was started at about 120C. the followlng morning, and exotherm again was observed, as well as good activity.
(A slow constant feed was tried at a couple points during the reaction with good results - fairly stable pressure.) The pressure built up eventually, so the constant feed was stopped (ethylene oxide was not consumed rapidly enough). Addition of ethylene oxide was difficult at the end of reaction due to high reactor pressure (higher than the feed). The liquld product was clear and colorless, and had a pH of 6. The catalyst was filtered out using No~ 1 filter paper and then an F
sintered glass funnel. The product was analyzed using vapor phase chromatography. The catalyst was rinsed out of the bottom of the bomb with about 100 ml. of distilled water. The pH of the wash water was 6 and the ~L~Z~313~X

pH of the catalyst was 5. The catalyst was light brown.
The catalyst was calcined in a Pyrex tube at 575C.
(~with alr ~low) for 1 hour and then stored in a desiccator. The pH of the calcined catalyst in water was 2 to 3. The product was CARBOWAX~ polyethylene glycol 200 prepared by the ethoxylation of ethylene glycol.

Preparatlon Of CARBOWAX~ Polyethylene Glycol 200 Using Phosphate-Bound Zirconium Oxlde Catalyst 50.8 g of ethylene glycol and 4.56 g of phosphate-bound zirconium oxide catalyst (which had been recovered and recalcined ln Example 20) were charged to a Parr bomb. The pH of the mixture was 5. (The pH of ethylene glycol by itself was 6.) The following calculation determined the amount of ethylene oxide needed:

62.07 g 163.69 ~ (product) - 50.80 g Y = 112.89 g of Ethylene Oxlde The bomb was purged with N2 and evacuated three times.

12~33092 The bomb was left under 16 p.s.i.g. of N2. The bomb was heated to 120C., stirred vigorously. Ethylene oxide w~as charged to the bomb based on the following schedule:

_ TABLE XII

Reactor Total Top Of Time, Reactor Pressure, Oxide Feed, Exotherm, Mins. Temp.,_C. p.s.l g. grams C.
o 126 24/54 5.4 135C
120 26/58 9.8 131 9 121 28/58 13.6 130 13 121 28/60 18.0 131 18 120 28/60 21.5 130 24 119 29/60 24.8 132 0 121 30/62 27.6 129 34 120 31/60 30.1 125 38 120 32/64 32.7 126 43 119 32 (1) 136 121 56 (2)77.4 225 120 46 (3) 267 121 56 84.0 282 120 49/56 85.o 305 120 49/60 86.1 312 120 51/62 87.4 ~830912 318 120 ~4/66 88.3 332 120 50/68 89.5 3,55 121 50/62 90.8 367 120 51/66 92.2 37~ 120 55/66 93.1 403 120 52/65 94.1 415 121 52/66 95.3 420 120 55/66 95.8 445 120 52 (4) 10 445 1~ 36 (5) 447 128 51/60 ~9.5 488 (6) 121 54/60 99.7 Notes:
1. Started constant feed of ethylene oxide.
2. Stopped constant feed of ethylene oxide.
3. Resumed making ethylene oxide additions.
4, Shut off reactor heat and allowed to set overnight.
5. Resumed heating reactor.
20 6. Run was shut down shortly thereafter.

The reaction was started at about 120C. An exothe~m was observed when ethylene oxide was added and the reaction rate was readily comparable to Example 21.

~'Z~;30~3~

Exotherms contlnued for several additions of ethylene oxide. After 38 minutes of the run, a constant ~eedlng o~ ethylene oxide at a rate of 1 g per 1.5 minutes was conducted. The reactor pressure at the start of the co~stant feed was 43 p.s.i. The reaction slowed as the total ethylene oxide feed approached 80 g. The feed rate had to be slowed as the pressure built up. The same happenlng had been observed ln Example 21. It was not clear whether the slow down of the activity was due to catalyst lnactivity, dilution effect (increased volume of liquid vs. fixed amount of catalyst), o~ hlgh bomb pressure. The liquld product was clear and colorless and had a pH of 6. The liquid product was poured from the bomb. The product was analyzed using vapor phase chromatography. CARBOWAX~ polyethylene glycol 200 was not quite produced because not quite enough ethylene oxlde was added. The purpose of this example is to see if the recovered and recalcined catalyst could be used to produce CARBOWAX~ ethylene glycol 200.

P~reparation Of CARBOWAX~ Polyethylene Glycol 400 Using Sulfate-Bound Zirconium Oxide Catalyst , 42.0 g of CARBOWAX~ polyethylene glycol 200 and 3.81 g of sulfate-bound zlrconium oxide catalyst were ; charged to a Parr bomb~ The bomb was purged with N2 and evacuated three times. The bomb was left under 16 p.s.l.g. of N2. The bomb was heated to 65C. and stirred vlgorously. The catalyst used in thls reactlon was less acidlc than others used ln some of these examples. Also the starting reactlon was a lower temperature to try to ellminate high exotherms and possible color problems. Ethylene oxide was charged to the bomb based on the following schedule:

Reactor Total Ethylene Time, Reactor Pressure, Oxide Feed, Mins. Temp., C. p.s.i.g. grams 0 65 l9/37 6.3 20 8 65 32/43 9.9 18 62 40 (l) 37 129 34/50 12.5 33~

43 118 36/52 15.2 54 120 36/52 18.0 6~1 119 36/53 20.4 69 120 38/55 22.9 80~ 120 39/55 23.0 ; 89 120 39/56 27.
100 120 40 (2) 100 18 19 (3) 116 65 22/35 32.8 138 129 52 (4) 145 122 40/58 34.2 151 124 40/58 35.9 155 131 40/58 37.7 172 125 40/70 39.4 183 121 38/68 40.8 193 124 40/58 42.0 230 123 36 (5) Notes:
~` 1. Reactor temperature was ralsed to about 120C.
2. Reactor was shut down overnight.
3. Reactor was restarted.
4. Temperature was raised to about 120C.

1!33~

5. The heat was turned offO

~here was very llttle exotherm on the lnitial ethylene oxide addition. Also~ the reactlon was slow at 65C., so the temperature was raised to about 120C. The reactlon rate was much faster, but stlll no exotherm was observed when ethylene oxide was added. The reaction was stopped overnlght. At that point, the liquid product was clear and colorless, and had a pH of 6. The reaction restarted a-t 65C. to try to avold high temperature operatlon and possible decomposltion. After adding a small amount of ethylene oxide, the temperature was raised to about 120C. (At one point in the run, the temperature reached 135 to 136C. fo~ about 5 minutes.) After the lnitial slight exotherm, no further exotherms we~e detected. The reaction was slow toward the end. The reaction was stopped and the gaseous ethylene oxide was removed. The liquld product was light yellow and had a pH of 6. The (pinkish brown) catalyst was ~iltered off. The catalyst was washed with 150 ml of distilled water, which resulted in a white catalyst. The pH of the water was 3 to 4 and of the catalyst ln the water was 3. The catalyst was light - yellow in water and was white when dry. The molecular weight of the product was too high and possibly the gas .. ~

~2~3~92 chromatography column might be plugged, so no vapor phase chromatography analysis was made. The catalyst ~as calcined ln a Pyrex tube at 575C, (with air flow) for 3.5 hours.
., Hydrolysis Of ~thylene Oxlde Using Sulfate-Bound Zlrconlum Oxide Catalyst 40.0 g of water and 3.30 g of sulfate bound zirconlum oxlde catalyst (the recovered, recalcined catalyst from Example 23) were charged to a Parr bomb.
The bomb was purged with N2 and evacuated three times.
The bomb was left under 16 p.s.i.g. of N2. The bomb was hated to about 800C. and stlrred vigorously. Ethylene oxlde was charged to the bomb based on the following scheduie TABLE XIV

Reactor Total Ethylene Time, Reactor Pressure Oxide Feed~
Mins. Temp., C. p.s.i.~ grams 20 o 78 22/38 3.3 ~2~33092 79 31/42 6.o 24 78 26/43 9.3 3'5 79 29/44 13.4 79 26 (l) , 18 17 (2) 102 30/54 17.6 58 100 34/50 19.9 62 105 38/58 21.6 64 106 38/56 23.1 ; 10 66 105 38/58 24.1 68 104 38/54 26.6 72 103 38/58 28.2 74 104 38/56 30.1 78 103 38/58 32.0 82 105 38/58 34.0 102 38/58 35.5 88 101 38/58 37.o 91 99 38/59 38.9 94 100 38/59 41.2 ~0 99 100 38/59 43.2 103 99 38/59 45.3 105 99O 38/58 46 ~ 9 109 99 38/59 49.0 Notes:

33~2 l. Heat was turned off overnight.
2. Heat was applied again next day.

No exotherms were observed until the temperature was ralsed to about 100C. Small exotherms (2 to 5C.) were observed therea~ter when ethylene oxide was added.
The rate of reaction was fast;er at 100C., and remained fairly fast throughout the reactlon. The reaction was stopped, the bomb was evacuated and the catalyst was filtered out. The liquld product was clear and colorless, although some of the catalyst remained in the product. The product had a pH of 4 to 5. 25.56 g of water was removed from the product on a Rotavapor at 90C. and 30 inches of vacuum. 20.54 g of product remalned as a kettle product. 75 ml of ethyl acetate was added to the kettle product in a separation funnel but layers were evldent. The material was removed and drled over anhydrous MgS04 (no clumping was observed).
The solution was filtered and the ethyl acetate was removed in vacuo from the solid filtrate. The solid product was analyæed using vapor phase chromatography.
The product was hydrolyzed ethylene oxide (ethylene glycol, dlethylene glycol, and triethylene glycol).

,~

,; ': ' ~2~3~g~

Ethoxylation Of l-Butanol Using Sulfate-Bound Zirconium Oxi~de Catalyst 74.1 g (1 mole) of l-butanol nd 3.30 g of sulfate-bound zirconium oxlde catalyst were charged to a Parr bomb. (The catalyst had been prepared by the procedure of Example 1.) The bomb was purged with N2 and evacuated three times. The bomb was left under 16 p.s.i.g. of N2. The bomb was heated to about 100C. and stirred vigorously. The pH of the materlal ln the bomb was 6. Ethylene oxide was charged to the bomb based on the rollowing schedule: -TABLE XV

Reactor Total Ethylene Time, Reactor Pressure Oxide Feed, Mins. Temp.~ C. p.s.i.g. ~rams O 112 24/33 5.5 17 110 33/42 ~.7 33 109 34/42 11.0 ~LZ !33~9.~2 Once ethylene oxide was added, the reaction proceeded s~owly. The reaction was kept at 109C. for two hours after the last ethylene oxide addltlon, and then the reactor system was shut down. A total of 11 grams of ethylene oxide were used, so the molar ratio o~
l-butanol to ethylene oxlde was 4 to 1. The product was clear and colorless and had a pH of 6. The catalyst was filtered off. The catalyst was placed in a Pyrex tube and calclned at 575C. (with air flow) for 3.5 hours.
The pH of the catalyst in water was neutral. The product was ethoxylates of l-butanol.

Ethoxylation Of l-Butanol Uslng Sulfate-Bound Zirconium Oxlde Catalyst 74.1 g (1 mole) of l-butanol and 5.20 g of sulfate-bound ~lrconium oxide catalyst (which had been recovered and recalcined in Example 25) were charged to a Parr bomb. The bomb was purged with N2 and evacuated three times. The bomb was left under 16 p.s.i.g. of N2.
The bomb was heated to 80oC. and stirred vigorously.
The pH of the material in the bomb was 6. Ethylene .
.

, ' ,, :

~2~33~

oxide was charged to the bomb based on the following schedule:

TABLE XVI

Reactor Total Ethylene Time, Reactor Pressure Oxide Feed, Mins. Temp., C. p.s.i.g. grams 81 19/33 6.6 7 (1) 32 110 40/45 9.8 10 15 108 I~o/46 11.1 .

Note:

1. Raised temperature of the reactor.
"

Once ethylene oxide was added, the reaction proceeded slowly and no exotherm was noticed. So the temperature was raised to 110C. and the reactlon rate inc.eased.
No exotherms were noticed at the higher temperature level. The reactor system was shut down. A total of 11.1 g of ethylene oxlde were used, so the molar ratio Of l-butanol to ethylene oxide was 4 to 1. The liquid product was clear and colorless and had a pH of 6. The ~283C~9;~:

catalyst was filtered off. The product was analyzed by vapor phase chromatography. The excess catalyst was r~nsed (but not washed) from the bomb using acetone.
The catalyst was calcined ln a Pyrex tube at 575C.
(wi-th air flow) for 3 hours. The pH of the calclned catalyst was neutral. The product was ethoxylates Or l-butanol.

Ethoxylation Of Glycerol Uslng Sulfate-Bound Zirconlum Oxide Catalyst 60.2 g of anhydrous glycerol and 3.0 g of sulfate-bound zirconium oxlde catalyst were charged to a Parr bomb. (The catalyst had been prepared by the ; procedure of Example 1.) The bomb was purged with N2 and evacuated three tlmes. The bomb was left under 16 p.s.i.g. of N2. The bomb was heated to 80C. and ; stirred vigorously. The pH of the material ln the bomb was 5 to 6. Ethylene oxlde was charged to the bomb based on the follow~ng schedule:

- : ..,..,... ~ , ~.... ~ .
- :

~.283~2 ~7 TABLE XVII

Reactor Total Ethylene Top Of Time, Reactor Pressure, Oxide Feed, Exotherm, Mi~s. Temp., C. p.s.i.g. grams C.

81 18/57 3.4 ~6 6 80 36/58 6.7 860 13 79 42/56 9.3 86 78 44/56 11.7 87 26 78 42/56 14.2 89 10 35 80 40/54 17.3 83 ~2 44/54 19.6 59 80 29/47 22.0 A small exotherm (about 6C.) was observed for the first few additions of ethylene oxide. The reaction rate was slower than with ethylene glycol, but lt still was fairly fast. The liquid product was clear and colorless, and had a pH of 5. The catalyst was flltered off, but the filtration was very difficult because the ~o liquid product was very thick (viscous). The product was analy~ed by vapor phase chromatography. The catalyst was washed with about 200 ml of distilled water ., :

~L283 [11~'2 and placed ln a test tube. The product was ethoxylated glycerol.

Ethoxylation Of l-Butanol Uslng Sulfate-Bound Zirconlum Oxide Catalyst 74.1 g (1 mole) of l-butanol and 3.0 g of sulfate-bound ælrconium oxlde catalyst were charged to a Parr bomb. (The catalyst had been prepared by procedure of Example 1.) The bomb was purged wlth N2 and ; 10 evacuated three times. The bomb was left under 16 p.s.i.g. of N2. The bomb was heated to 110C. and stirred vigorously. The pH of the material in the bomb was 5 to 6. Ethylene oxide was charged to the bomb based on the followlng schedule:

TABLE XVIII

Reactor Total Ethylene Time, Reactor Pressure, Oxide Pressure, Mlns. Temp., C. p.s.i.~ grams 0 110 22/32 5.3 110 32/40 8.4 , . ' , - .
~' ` `'', :

12~3~9~, 31 109 33/42 11.2 J

The ~eaetion rate was fairly slow but was eomparable wit-h other l-butanol runs. The reactor was shut down, and the catalyst was filte~ed out o~ the liquid product.
79.52 g of the llquid product was obtained. A total of 11.2 g of ethylene oxide was usedl so the molar ratio of 1-butanol to ethylene oxlde was 4 to 1. The liquid produet was elear and eolorless and had a pH of 5 to 6.
The liquld product was analyzed by vapor phase chromatography.
40 g of the llquid produet was dlstilled in the fractionating column having a small eondensor. The fraetions of the distillation were:

TABLE XIX

Pereent Fractlon Temp., C~ Wt. g. Of Total Product l-Bu~anol 11727.39 69.4 Butyl Cellosolve~ 171 7.46 18.9 Product 4.61 11.7 (higher ethoxylates) Total - 39.46 100 ~33~2 28.71 g of the llquid product was separated lnto 1-butanol and butyl cellosolve on a Rotavapor.
(c'ondltions: 60C. on water bath, vacuum pump on condensor). The fractions were:

TABLE XX
.

; 1 Percent Receiver Wt., g Of Total Product Butanol 16.90 65.5 Kettle Product Butyl Cellosolve Higher Ethoxylates 8.92 34.5 Total -25.82 100 Note:
1. Probably lost some product to the vacuum.

Calcining Commerical Zirconlum Sulfate Oxide Commercial zirconlum sulfate oxide was placed in a Pyrex tube and calcined at 800C. (with air flow) for 2 3/4 hours. The pH of the catalyst after calcining was 2. The calcined catalyst was insoluble in water.

~ ' ~

1~830~ UD 13928 :

Preparation Of CARBOWAX~ Polyethylene Glycol Using Calclned Commercial Zlrconium Sulfate Oxide 40~0 g of ethylene glyco:L and 2.5 g of` the calclned commercial zlrconlum sulfate oxlde from Example 29 were charged to a Parr bomb. The ~ormula for commerclal zirconlum sulfate oxide ls ZrO(S04).H2S04.3H20. The bomb was purged with N2 and evacuated three tlmes. The bomb was left under 16 p.s.l.g. of N2. The bomb was heated to 80C. and stlrred vigorously. The pH of the material in the bomb was 5. Ethylene oxide was charged to the bomb based on the following schedule:

TABLE XXI

Reactor To~al Ethylene Top Of 15 Tlme, Reactor Pressure, Oxide Feed, Exotherm, Mins. Temp., C. p.s.l.~ grams C.
0 79 18/32 5.0 91 7 ~3 24/44 11.4 106 ~ 11 79 25/40 16.3 87 ;~ 20 18 820 30/46 22.1 (1) 27 81 28/46 29.5 .

~28301~Z

66 80 24/44 35.2 ~5 76 83 38/54 40.0 1~9 83 38 , Note:
1. No exotherm was noticed.

Exotherms were observed upon the first few additions of ethylene oxide. The reaction rate was slower than the sulfate-bound zlrconium oxide catalysts prepared in the above examples, but it was still fairly fast. The reactor was shut down and the catalyst was filtered from the liquid product. The liquid product was clear and colorless, and had a pH of 5 to 6. The product was analyzed by vapor phase chromatography. Catalyst was rinsed from the bomb. The catalyst was calcined in a Pyrex tube at 575C. (wlth a~r flow) for l hour. 2.05 g of catalyst was recovered. The pH of the catalyst in water was about 6. The product was CARBOWAX~
polyethylene glycol prepared by the ethoxylation of ethylene glycol.

.

l3309~

Preparation of Sulfuric Acid - Treated Zirsil* 401 Catalyst Zirsil* 401 (from Magnesium Elektron, Inc.) was dried at 100C. in an open beaker over a weekend. 25 g. of the dried white powder was treated with 375 ml. of 1 N H2SO4 in a beaker with stirring for about 5 minutes. The admixture was filtered. The solid filtrate was dried at 100C. for 1.5 hours. The solid was calcined in Pyrex* tubes at 575C. (with air flow ) for 2 hours. Zirsil* 401 is a composition which includes 52 percent of silicon oxide, 16 percent of hydrous zirconium oxide, 12 percent of zircon, 2 to 3 percent of sodium iron at 120 ppm and titanium at 150 ppm, which has an ignition loss at 1000C. for one hour of 20 percent (mostly water), and which has a free moisture at 150C. for 15 minutes of 12 percent.

*Trademark.

~2~ Z

' Preparation Of Baslc Sulfate-Bound Zirconium Oxide Cat21yst 35.0 g of baslc sulfate-bound zlrconium oxlde (which had a pH of 2 in water) was placed ln a crucible wlth the lid aJar and was calclned at 800C. (with alr flow) for 3 hours. The pH of the catalyst ln water was ?

Treatment Of Sulfate-Bound Zirconium Oxide Catalyst With Sodium Hydroxide 3.85 g of sulfate-bound zirconlum oxide catalyst (which had a pH of 2 in water) was treated with 50 ml of 0.5 N NaOH solution in a beaker with stlrring for about 1 minute. (The catalyst had been prepared by the procedure of Example 1.) The admixture was flltered.
..
The solid flltrate was calcined in a Pyrex tube at 575C. (wlth alr flow) for 1 hour. The pH of the . .:

,', ~, ,' ~2~33(~92 calclned catalyst in water was 9.

' EXAMPLE 34 Preparation Of CARBOWAX~ Polyethylene Glycol Using Basic Sulfate-Bound Zirconium Oxide Catalyst 540.1 g of ethylene glycol and 5.0 g of the basic sulfate-bound zlrconium oxide catalyst Or Example 33 were charged to a Parr bomb. The bomb was purged with N2 and evacuated three tlmes. The bomb was left under 16 p.s.i.g. of N2. The bomb was heated about 850C. and stlrred vigorously. The pH of the materlal in the bomb was 5 to 6. Ethylene oxide was charged to the bomb based on the following schedule:

TABLE XXII
-- .

Reactor Total Ethylene ~ 15 Time~Reactor Pressure Oxide Feed, : Mins. Temp., C. p.s.i.~ ams o 85 18/46 5.9 : 25 105 23/54 9.5 ' 43 110 24/56 13.8 :~ 20 63 112 25/50 16.7 :~`

~2~33(~

73 110 30/58 19.1 112 32/54 20.6 98 111 28/58 22.7 106 111 33 (1) 106~ 115 25/54 27.4 151 110 27/64 31.5 206 110 28/62 35.5 247 110 33/68 40.5 Note:
1. The reactor heat was cut off and the reactor sat overnight.
, No exotherm was notlced after the flrst ethylene oxide addition. After the second ethylene oxide addition, there was an exotherm to 123C. but there was no reaction after 5 minutes because there was no pressure drop. The pressure was increased to 110C. and there was an exotherm to 114C. The reactor was shut down after the run. The catalyst was filtered out of the liquid product and placed ln a test tube.

. . .

-- ~2831D92 Hydrolysis of Zirconyl Acetate To Produce Sulfate-Bound Zirconum Oxide Catalyst 30 g of (NH4)2SO~ were dissolved in 100 ml of distilled water. 11.26 g of zirconyl acetate, i.e., ZrO(OAc)2 where OAc is C2H3O2, was added to the solution. An additional 50 ml of distilled water was added. At this point, the pH of the solution was ~ to 5. A total of 9.5 ml o~ 4M
NaOH was added to the solution to raise the pH to 9.
The solid material was filtered out of the solution and washed with acetone. The solid was calcined in Pyrex* tubes at 575C. (with air flow) for 3.5 hours. The pH of the calcined solid in water was 1.
2 grams of the calcined material was set aside for later use. The remainder of the calcined material was washed with about 200 ml of distilled water and th~n rinsed with acetone to dry it. The material was then calcined in a Pyrex* tube at 520C. (with air flow) for 23 hours. The pH of the solid in water was 1 to 2. The solid was sulfate-bound zirconium oxide catalyst.

*Trademark.

~.' ~2~33~2 P~eparation Of CARBOWAX~ Polyethylene Glycol Uslng Sulfate-Bound Zirconium Oxide Catalyst 40.0 g of ethylene glycol and 2.0 g of sulfate-bound zirconlum oxide catalyst (that whlch was set aside ln Example 35 for a later use) were charged to a Pa~r bomb. The bomb was purged with N2 and evacuated three tlmes. The bomb was left under 16 p.s.l.g. of N2.
The bomb was heated to about 80C. and stirred vigorously. The pH of the material in the bomb`
initlally was 5, but the pH stick slowly changed to 2.
Ethylene oxlde was charged to the bomb based on the following schedule:

.
` TABLE XXIII

Reactor Total Ethylene Top Of Time, Reactor Pressure, Oxide Feed~ Exotherm, Mins. Temp., C. p.s.iog. grams C.

0 82 20/42 5.7 108 4 91 29/50 10.6 (1~

11 91 30/45 16.0 (1) 108 2~/55 20.0 128 31 110 32/55 23.6 119 ~L2133~

37 103 32/60 27.5 130 (1) 47 112 34/60 30.2 124 (1) 54 112 36/60 34.7 117 (1) 67 109 34/60 40,0 An exotherm was observed upon the flrst ethylene oxide addition, and the reactlon rate was fairly fast. At the 25 mlnute addition, the reaction temperature was raised to about 110C. Thereafter, mild exotherms occurred and the reaction rate remained fairly fast. After the ~eactor was closed down, the catalyst was filtered out of the liquid product and discarded. The pH of the liquid product was 5. The liquid product was analyzed ; uslng vapor phase chromatography~ The CARBOWAX~
polyethylene glycol product conta1ned a large amount of undeslrable 1,4-dioxane.

Hydrolysis Of Hafnyl Chlorlde To Product Sulfate-Bound Hafnyl Oxide Catalyst 16.4 g of HfOC12.8H20 were dissol~ed in 100 ml of distilled water. The pH of the solution was 0 to 1.

lZ~3~9;~

Concentrated NH40H was added, with stirring, until the solution pH reached 9 and a whlte, gelatinous precipitate formed. 6 ml of MH40H were added to the solution, which was stirred for 10 minutes. The product precipitated out of the solution. The solid filtrate was washed overnight in a Soxhlet extractor wlth distllled water. The wash water in the Soxhlet extractor with the catalyst had a pH of 7 and was negative for Cl (AgN03 test). The wash water in the flask had a pH of 7 and tested positive for Cl . The solid was dried in an open beaker set in an oven (100 to 120C.) for about 24 hours. 7.05 g of solid was obtained. The solid was treated with 106 ml of lNH2S04 in a beaker with stirring for about 5 minutes. The solid was dried overnight at 110 to 120C. The pH of the solid in water was 2. The solid was calcined in a Pyrex tube at 575C. (with air flow) for 4.5 hours. The resultant fine white powder had a pH of 1 in water. The solid was sulfate-bound hafnyl oxide catalyst.

lZ~331D9~
~D 13928 Preparation Of CARBOWAX0 Polyethylene Glycol Uslng Sulfate-Bound Hafnyl Oxide Catalyst 40.0 g of ethylene glycol and 2.0 g of sulfate-bound hafnyl oxide catalyst (as prepared in Example 38) were charged to a Parr bomb. The bomb was purged with N2 and evacuated three times. The bomb was left under 16 p.s.i.g. of N2. The pH of the material ln the bomb was 3 (and was slow to change). The bomb was heated to 100C. and stirred vigorously. Ethylene oxide was added to the bomb based on the following schedule:

TABLE XXIV
.
Reactor Total Ethylene Top Of Time, Reactor Pressure, Oxide Feed, Exotherm~
15 Mins. Temp., _C. p.s.i.g. grams C.

0 100 21/46 5.4 134 3 110 28/50 10.2 136 111 2~/50 15.1 135 8 111 30/50 20.2 135 20 10 111 30/50 25.3 130 13 109 32/50 30.1 124 .~ .
.. ~ ....
~,. . .
. .

~LZ~331[)~7~

16 109 33/50 33.0 116 111 33/50 35-l~ 115 23 110 34/52 37.7 113 109 35/50 40.0 (1) 49 ~ 110 35 Note:
1. No exotherm.

The reactlon was run at 100 to 110C. Fairly large exotherms occurred run when ethylene oxide was added.
The reaction rate was very fast (when compared to the fastest zlrconium compound catalyst tested in the above examples). The catalyst was filtered from the product, and washed with about 25 ml of methanol. The catalyst was placed in a Pyrex test tube and placed in a 530C.
oven (with air flow) for about 12 days. The llquid product was analyzed using vapor phase chromatography.
The product contained a fairly large amount of dioxane.
The product was CARBOWAX~ polyethylene glycol produced by ethoxylation of ethylene glycol.

~ : ' ~ .

Claims (76)

1. Process for alkoxylating active-hydrogen compounds, comprising reacting a liquid or solid epoxide compound having the formula:

wherein R1, R2, R3 and R4 are each H or -(CH2)nCH3, and wherein n is 0 to 3, with the proviso that R1, R2, R3 and R4 can be the same or different, with the active-hydrogen compound, said active-hydrogen compound being in the liquid or gaseous state, in the presence of a catalytic amount of at least one solid anion-bound metal oxide heterogeneous catalyst, wherein said anion in said anion-bound metal oxide heterogeneous catalyst is SO4, BF4, CO3, BO3, HPO4, SeO4, MoO4, B4O7 or PF6, and the metal oxide is zirconium oxide, nickel oxide, aluminum oxide, tin oxide, calcium oxide, magnesium oxide, iron oxide, titanium oxide, thorium oxide, hafnium oxide or rubidium oxide, said anion-bound metal oxide heterogeneous catalyst being an amorphous or primarily amorphous compound, and said active-hydrogen compound not poisoning said anion-bound metal oxide heterogeneous catalyst.

2. Process as claimed in Claim 1 wherein the epoxide compound is ethylene oxide or propylene oxide.

3. Process as claimed in Claim 1 wherein 0.5 to 50 weight percent, based on the total weight of said epoxide compound and said active-hydrogen compound, of said anion-bound metal oxide catalyst is used.

4. Process as claimed in Claim 1 wherein said solid anion-bound metal oxide catalyst is an anion-bound zirconium oxide catalyst, an anion-bound nickel oxide catalyst, an anion-bound aluminum oxide catalyst, an anion-bound tin oxide catalyst, an anion-bound calcium oxide catalyst, an anion-bound magnesium oxide catalyst, an anion-bound rubidium oxide catalyst, an anion-bound titanium oxide catalyst, an anion-bound thorium oxide catalyst, an anion-bound hafnium oxide catalyst or an anion-bound iron oxide catalyst.

5. Process as claimed in Claim 1 wherein said catalyst is a solid anion-bound zirconium oxide catalyst.

6. Process as claimed in Claim 5 wherein said solid anion-hound zirconium oxide catalyst contains about 2 to about 3 weight percent, based on the total weight of said catalyst, of said anion.

7. Process as claimed in Claim 1 wherein said catalyst is a solid anion-bound thorium oxide catalyst.

8. Process as claimed in Claim 1 wherein said catalyst is a solid sulfate-bound hafnium oxide catalyst.

9. Process as claimed in Claim 1 wherein said catalyst is supported on an inert carrier.

10. Process as claimed in Claim 1 wherein an inert liquid diluent is also present.

11. Process as claimed in Claim 1 wherein said reaction is continuously conducted in a fixed-bed reactor.

12. Process as claimed in Claim 1 wherein said reaction is continuously conducted in a fluidized reactor.

13. Process as claimed in Claim 1 wherein said active-hydrogen compound is a thiol, a carboxylic acid, a sulfonic acid or a hydroxyl-containing compound.

14. Process as claimed in Claim 13 wherein said hydroxyl-containing compound is a primary monohydric alcohol, a secondary monohydric alcohol, a dihydric alcohol, a trihydric alcohol, a polyhydric alcohol, an alkoxylated ethylene glycol or a glycol ether.

15. Process as claimed in Claim 13 wherein said hydroxyl-containing compound is a primary monohydric alcohol containing 1 to 12 carbon atoms or a secondary monohydric alcohol containing 2 to 12 carbon atoms.

16. Process as claimed in Claim 13 wherein said hydroxyl-containing compound is an aliphatic diol which contains 1 to 12 carbon atoms, an aromatic diol which contains 4 to 20 carbon atoms or a heterocyclic diol which contains 1 to 20 carbon atoms.

17. Process as claimed in Claim 16 wherein said aliphatic diol is ethylene glycol.

18. Process as claimed in Claim 13 wherein said hydroxyl-containing compound is a trihydric alcohol containing 1 to 12 carbon atoms.

19. Process as claimed in Claim 13 wherein said hydroxyl-containing compound is glycerol, an alkoxylated ethylene glycol or a glycol ether.

20. Process as claimed in Claim 1 wherein said anion-bound metal oxide is removed from the reaction site and is regenerated by calcination in air or oxygen at a temperature of 300°C to 950°C for a period of 1 to 4 hours.

21. Process as claimed in Claim 20 wherein said temperature is between 500°C and 800°C.

22. Composition comprising (a) liquid or solid epoxide compound having the formula:

wherein R1, R2, R3 and R4 are each H or -(CH2)nCH3, wherein n is 0 to 3, with the proviso that R1, R2, R3 and R4 can be the same or different, (b) an active-hydrogen compound, said active-hydrogen compound being in the liquid or gaseous state, and (c) a catalytic amount of at least one solid anion-bound metal oxide heterogeneous catalyst, wherein said anion in said anion-bound metal oxide heterogeneous catalyst is SO4, BF4, CO3, BO3, HPO4, SeO4, MoO4, B4O7 or PF6, and the metal oxide is zirconium oxide, nickel oxide, aluminum oxide, tin oxide, calcium oxide, magnesium oxide, rubidium oxide, titanium oxide, thorium oxide, hafnium oxide or iron oxide, said anion-bound metal oxide heterogeneous catalyst being an amorphous or primarily amorphous compound, and said active-hydrogen compound not poisoning said anion-bound metal oxide heterogeneous catalyst.

23. Composition as claimed in Claim 22 wherein the epoxide compound is ethylene oxide or propylene oxide.

24. Composition as claimed in Claim 22 wherein said active-hydrogen compound is a thiol, a carboxylic acid, a sulfonic acid or a hydroxyl-containing compound.

25. Composition as claimed in Claim 24 wherein said hydroxyl-containing compound is a primary monohydric alcohol, a secondary monohydric alcohol, a dihydric alcohol, a trihydric alcohol, a polyhydric alcohol, an alkoxylated ethylene glycol or a glycol ether.

26. Composition as claimed in Claim 25 wherein said hydroxyl-containing compound is a primary monohydric alcohol containing l to 12 carbon atoms or a secondary monohydric alcohol containing 2 to 12 carbon atoms.

27. Composition as claimed in Claim 25 wherein said hydroxyl-containing compound is an alkoxylated ethylene glycol or a glycol ether.

28. Composition as claimed in Claim 22 wherein 0.5 to 50 weight percent, based on the total weight of said epoxide compound and said active-hydrogen compound, of said anion-bound metal oxide catalyst is present.

29. Composition as claimed in Claim 22 wherein said catalyst is a solid anion-bound zirconium oxide catalyst.

30. Composition as claimed in Claim 30 wherein said solid anion-bound zirconium oxide catalyst contains about 2 to about 3 weight percent, based on the total weight of said catalyst, of said anion.

31. Composition as claimed in Claim 22 wherein said catalyst is a solid anion-bound thorium oxide catalyst.

32. Composition as claimed in Claim 22 wherein said catalyst is a solid sulfate-bound hafnium oxide catalyst.

33. Composition as claimed in Claim 22 wherein said catalyst is supported on an inert carrier.

34. Composition as claimed in Claim 22 wherein an inert liquid diluent is also present.

35. Process comprising reacting at least one molecule of a liquid or solid epoxide compound having the formula:

wherein R1, R2, R3 and R4 are each H or -(CH2)nCH3, and wherein n is 0 to 3, with the proviso that R1, R2, R3 and R4 can be the same or different, with at least one other molecule of said epoxide compound in the presence of a catalytic amount of at least one solid anion-bound metal oxide heterogeneous catalyst, wherein said anion in said anion-bound metal oxide heterogeneous catalyst is SO4, BF4, CO3, BO3, HPO4, SeO4, MoO4, B4O7 or PF6, and the metal oxide is zirconium oxide, nickel oxide, aluminum oxide, tin oxide, calcium oxide, magnesium oxide, iron oxide, titanium oxide, thorium oxide, hafnium oxide or rubidium oxide, said anion-bound metal oxide heterogeneous catalyst being an amorphous or primarily amorphous compound, and said molecules of said epoxide compound can be the same epoxide compound or different epoxide compounds.

36. Process as claimed in Claim 35 wherein 0.5 to 50 weight percent, based on the total weight of said epoxide compound, of said anion-bound metal oxide catalyst is used.

37. Process as claimed in Claim 35 wherein said anion-bound metal oxide catalyst is an anion-bound zirconium oxide catalyst, an anion-bound nickel oxide catalyst, an anion-bound aluminum oxide catalyst, an anion-bound tin oxide catalyst, an anion-bound calcium oxide catalyst, an anion-bound magnesium oxide catalyst, an anion-bound rubidium oxide catalyst, an anion-bound titanium oxide catalyst, an anion-bound thorium oxide catalyst, an anion-bound hafnium oxide catalyst or an anion-bound iron oxide catalyst.

38. Process as claimed in Claim 35 wherein said catalyst is a solid anion-bound zirconium oxide catalyst.

39. Process as claimed in Claim 33 wherein said solid anion-bound zirconium oxide catalyst contains about 2 to about 3 weight percent, based on the total weight of said catalyst, of said anion.

40. Process as claimed in Claim 39 wherein said catalyst is an anion-bound thorium oxide catalyst.

41. Process as claimed in Claim 35 wherein said catalyst is a solid sulfate-bound hafnium oxide catalyst.

42. Process as claimed in Claim 35 wherein said catalyst is supported on an inert carrier.

43. Process as claimed in Claim 35 wherein an inert liquid diluent is also present.

44. Process as claimed in Claim 35 wherein the epoxide compound is ethylene oxide or propylene oxide.

45. process as claimed in Claim 35 wherein said reaction is continuously conducted in a fluidized reactor.

\

46. Process as claimed in Claim 35 wherein said anion-bound metal oxide is removed from the reactions and is regenerated by calcination in air or oxygen at a temperature of 300°C to 950°C for a period of 1 to 4 hours.

47. Composition comprising (a) at least one liquid or gaseous epoxide compound having the formula:

wherein R1, R2, R3 and R4 are each H or -(CH2)nCH3, and wherein n is 0 to 3, with the proviso that R1, R2, R3 and R4 can be the same or different, and (b) a catalytic amount of at least one solid anion-bound metal oxide heterogeneous catalyst, wherein said anion in said anion-bound metal oxide heterogeneous catalyst is SO4, BF4, CO3, BO3, HPO4, SeO4, MoO4, B4O7 or PF6, and said metal oxide in said anion-bound metal oxide heterogeneous catalyst is zirconium oxide, nickel oxide, aluminum oxide, tin oxide, calcium oxide, magnesium oxide, rubidium oxide, titanium oxide, thorium oxide, hafnium oxide or iron oxide, said anion-bound metal oxide heterogeneous catalyst being an amorphous or primarily amorphous compound.

48. Composition as claimed in Claim 47 wherein the epoxide compound is ethylene oxide or propylene oxide.

49. Composition as claimed in Claim 47 wherein 0.5 to 50 weight percent, based on the total weight of said epoxide compound and said hydroxyl-containing compound, of said anion-bound metal oxide catalyst is used.

50. Composition as claimed in Claim 47 wherein said catalyst is a solid anion-bound zirconium oxide catalyst.

51. Composition as claimed in Claim 50 wherein said solid anion-bound zirconium oxide catalyst contains abut 2 to about 3 weight percent, based on the total weight of said catalyst, of said anion.

52. Composition as claimed in Claim 47 wherein said catalyst is a solid anion-bound thorium oxide catalyst.

53. Composition as claimed in Claim 47 wherein said catalyst is a solid sulfate-bound hafnium oxide catalyst.

54. Composition as claimed in Claim 47 wherein said catalyst is supported on an inert carrier.

55. Composition as claimed in Claim 47 wherein an inert liquid diluent is also present.

56. Alkoxylation process comprising reacting a liquid or gaseous epoxide compound having the formula:

wherein R1, R2, R3 and R4 are each H or -(CH2)nCH3, and wherein n is 0 to 3, with the proviso that R1, R2, R3 and R4 can be the same or different, with a sodium salt of an acid sulfate of a secondary monohydric alcohol having 10 to 20 carbon atoms, said secondary monohydric alcohol salt being in the liquid state, in the presence of a catalytic amount of at least one solid anion-bound metal oxide heterogeneous catalyst, wherein said anion in said anion-bound metal oxide heterogeneous catalyst is SO4, BF4, CO3, BO3, HPO4, SeO4, MoO4, B4O7 or PF6, and the metal oxide is zirconium oxide, nickel oxide, aluminum oxide, tin oxide, calcium oxide, magnesium oxide, iron oxide, titanium oxide, thorium oxide, hafnium oxide or rubidium oxide, said anion-bound metal oxide heterogeneous catalyst being an amorphous or primarily amorphous compound.

57. Process as claimed in Claim 56 wherein the epoxide compound is ethylene oxide or propylene oxide.

58. Process as claimed in Claim 56 wherein 0.5 to 50 weight percent, based on the total weight of said epoxide compound and said hydroxyl-containing compound, of said anion-bound metal oxide catalyst is used.

59. Process as claimed in Claim 56 wherein said anion-bound metal oxide catalyst is an anion-bound zirconium oxide catalyst, an anion-bound nickel oxide catalyst, an anion-bound aluminum oxide catalyst, an anion-bound tin oxide catalyst, an anion-bound calcium oxide catalyst, an anion-bound magnesium oxide catalyst, an anion-bound rubidium oxide catalyst, an anion-bound titanium oxide catalyst, an anion-bound hafnium oxide catalyst or an anion-bound iron oxide catalyst.

60. Process as claimed in Claim 56 wherein said catalyst is a solid anion-bound zirconium oxide catalyst.

61. process as claimed in Claim 56 wherein said catalyst is a solid anion-bound thorium oxide catalyst.

62. Process as claimed in Claim 56 wherein said catalyst is solid sulfate-bound hafnium oxide catalyst.

63. Process as claimed in Claim 56 wherein said catalyst is supported on an inert carrier.

64. Process as claimed in Claim 56 wherein an inert liquid diluent is also present.

65. Process as claimed in Claim 56 wherein said reaction is continuously conducted in a fluidized reactor.

66. Process as claimed in Claim 56 wherein said anion-bound metal oxide catalyst is removed from the reaction site and is regenerated by calcination in air or oxygen at a temperature of 300°C to 950°C for a period of 1 to 4 hours.

67. Composition comprising (a) a liquid or gaseous epoxide compound having the formula:

wherein R1, R2, R3 and R4 are each H or -(CH2)nCH3, and wherein n is 0 to 3, with the proviso that R1, R2, R3 and R4 can be the same or different, with a sodium salt of an acid sulfate of a secondary monohydric alcohol having 10 to 20 carbon atoms, said secondary monohydric alcohol salt being in the liquid state, and (b) a catalytic amount of at least one solid anion-bound metal oxide heterogeneous catalyst, wherein said anion in said anion-bound metal oxide heterogeneous catalyst is SO4, BF4, CO3, BO3, HPO4, SeO4, MoO4, B4O7 or PF6, and the metal oxide in said anion-bound metal oxide heterogeneous catalyst is zirconium oxide, nickel oxide, aluminum oxide, tin oxide, calcium oxide, magnesium oxide, rubidium oxide, titanium oxide, thorium oxide, hafnium oxide or iron oxide, said anion-bound metal oxide heterogeneous catalyst being an amorphous or primarily amorphous compound.

68. Composition as claimed in Claim 67 wherein the epoxide compound is ethylene oxide or propylene oxide.

69. Composition as claimed in Claim 67 wherein 0.5 to 50 weight percent, based on the total weight of said epoxide compound, of said anion-bound metal oxide catalyst is used.

70. Composition as claimed in Claim 67 wherein said catalyst is a solid anion-bound zirconium oxide catalyst.

71. Composition as claimed in Claim 67 wherein said catalyst is a solid anion-bound thorium oxide catalyst.

72. Composition as claimed in Claim 67 wherein said catalyst is a solid sulfate-bound hafnium oxide catalyst.

73. Composition as claimed in Claim 67 wherein an inert liquid diluent is also present.

74. Process as claimed in claim 1 wherein said solid anion-bound metal oxide heterogeneous catalyst is an anion-bound zirconium oxide catalyst, an anion-bound titanium oxide catalyst, an anion-bound iron oxide catalyst or an anion-bound thorium oxide catalyst.

75. Process as claimed in claim 74 wherein the epoxide compound is ethylene oxide or propylene oxide.

76. Process as claimed in claim 75 wherein the active-hydrogen compound is ethylene glycol.