FIELD OF THE INVENTION

[0001] This invention pertains to a process for the c/ tra/is-isomeration of cyclic diols. In particular, this invention pertains to a process for the of a 2,2,4,4- tetraalkylcyclobutane-l,3-diol in the presence of hydrogen and a catalyst comprising ruthenium deposited on a catalyst support material.

BACKGROUND OF THE INVENTION

[0002] Tetraalkylcyclobutane-l,3-diols can be important intermediates for producing a variety of polymeric materials which possess advantageous properties. For example, polyesters derived from dicarboxylic acids and 2,2,4,4-tetramethylcyclobutane-l,3-diol can possess higher glass transition temperatures, impact strength, weatherability, and hydrolytic stability in comparison to many other polyesters prepared from other commonly- used diols. Tetraalkylcyclobutane-l,3-diols can be prepared by the catalytic hydrogenation of the corresponding 2,2,4,4-tetraalkylcyclobutane-l,3-dione (I), as illustrated in Figure 1 in which R is an alkyl group.

[0003] Typically, the hydrogenation of 2,2,4,4-tetraalkylcyclobutane-l,3-diones produces the corresponding 2,2,4,4-tetraalkylcyclobutane-l,3-diols as a mixture of cis and trans isomers. For example, U.S. Patent No 3,190,928 dislcoses the hydrogenation of 2,2,4,4- tetramethylcyclobutane-l,3-dione using nickel- or ruthenium-based catalysts to produce 2,2,4,4-tetraalkylcyclobutane-l,3-diols with molar cisitrans ratios that can vary widely from about 0.5 to about 1.2. Also, catalysts that produce the most desirable ratio of cisitrans isomers may not give the best yields or highest rates of hydrogenation. The cisitrans isomer ratio of 2,2,4,4-tetraalkylcyclobutane-l,3-diols can influence important properties such as, for example, the glass transition temperature, impact strength, and crystallization rate of the polyester polymers prepared from them. A cisitrans ratio that varies widely, in turn, can give polyesters with inconsistent and/or undesirable properties. A process to isomerize 2,2,4,4-tetraalkylcyclobutane-l,3-diols, therefore, would be desirable in order to produce 2,2,4,4-tetraalkylcyclobutane-l,3-diols with consistent cis:trans ratios regardless of the hydrogenation catalyst used. Such an isomerization process also would enable the efficient production of polyesters from 2,2,4,4-tetraalkylcyclobutane-l,3-diols with properties that can be tailored to a variety of applications.

SUMMARY OF THE INVENTION

[0004] We have found that the cis-trans ratio of 2,2,4,4-tetraalkylcyclobutane-l,3-diols may be modified by contacting the diol with a supported ruthenium catalyst in presence of hydrogen. A general embodiment of our invention, therefore, is a process for the isomerization of a 2,2,4,4-tetraalkylcyclobutane-l,3-diol, comprising contacting a starting 2,2,4,4-tetraalkylcyclobutane-l,3-diol having a molar ratio of cis to trans isomers of 0:1 to about 1.5:1 with hydrogen in the presence of a catalyst comprising about 0.1 to about 10 weight percent ruthenium, based on the total weight of the catalyst, deposited on a support material, to produce an isomerized 2,2,4,4-tetraalkylcyclobutane-l,3-diol having a different molar ratio of cis to trans isomers that the starting 2,2,4,4-tetraalkylcyclobutane-l,3-diol, in which the process has no net production of 2,2,4,4-tetraalkylcyclobutane-l,3-diol.

[0005] Our process may be used, in particular, for the isomerization of 2,2,4,4- tetramethylcyclobutane-l,3-diol, and can be carried out under modest pressures and temperatures using a supported ruthenium catalyst containing about 1 to about 9 weight percent ruthenium. Thus, another aspect of the invention is a process for the isomerization of a 2,2,4,4-tetraalkylcyclobutane-l,3-diol, comprising contacting trans-2,2,4,4- tetramethylcyclobutane-l,3-diol with a catalyst comprising about 1 to about 9 weight percent ruthenium, based on the total weight of the catalyst, deposited on a support comprising silica, alumina, silica-alumina, titania, zirconia, activated carbon, graphitized carbon, carbon nanotubes, zeolites, chromia, rare earth metal oxides, or mixtures thereof at a pressure of about 0.4 to about 3.5 megapascals and a temperature of about 100 to about 250°C to form c/ ^' s-2,2,4,4-tetramethylcyclobutane-l,3-diol, in which the process has no net production of 2,2,4,4-tetraalkylcyclobutane-l,3-diol.

[0006] The process of the invention also can be used to convert a 2,2,4,4- tetramethylcyclobutane-l,3-diol having a low trans isomer content to an isomerized 2,2,4,4- tetramethylcyclobutane-l,3-diol having a greater amount of trans isomer. Another embodiment of our invention, therefore, is a process for the isomerization of a 2,2,4,4- tetraalkylcyclobutane-l,3-diol, comprising contacting a starting 2,2,4,4- tetraalkylcyclobutane-l,3-diol having a molar ratio of cis to trans isomers of 3:1 to about 20:1 with hydrogen in the presence of a catalyst comprising about 0.1 to about 10 weight percent ruthenium, based on the total weight of the catalyst, deposited on a support, to produce an isomerized 2,2,4,4-tetraalkylcyclobutane-l,3-diol having a molar ratio of cis to trans isomers of about 1.5 :1 to about 5 :1, wherein the process has no net production of 2,2,4,4-tetraalkylcyclobutane-l,3-diol.

DETAILED DESCRIPTION

[0007] We have found that the isomerization of 2,2,4,4-tetraalkylcyclobutane-l,3-diols such as, for example, 2,2,4,4-tetramethylcyclobutane-l,3-diol, can be carried efficiently in the presence of a supported ruthenium catalyst and hydrogen. The process provided by the present invention comprises the isomerization of a 2,2,4,4-tetraalkylcyclobutane-l,3-diol by contacting a starting 2,2,4,4-tetraalkylcyclobutane-l,3-diol having a molar ratio of cis to trans isomers of 0:1 to about 1.5:1 with hydrogen in the presence of a catalyst comprising about 0.1 to about 10 weight percent ruthenium, based on the total weight of the catalyst, deposited on a support, to produce an isomerized 2,2,4,4-tetraalkylcyclobutane-l,3-diol having a different molar ratio of cis to trans isomers than the starting 2,2,4,4- tetraalkylcyclobutane-l,3-diol. Our process has no net production of 2,2,4,4- tetraalkylcyclobutane-l,3-diol. Our process can be used, for example, to isomerize a trans- tetraalkylcyclobutane-l,3-diol to a c/ ^' s-tetraalkylcyclobutane-l,3-diol or vice versa. Our isomerization process can be operated independently of or in conjunction with the hydrogenation processes that are commonly used to prepare tetralkylcyclobutane-l,3-diols from the corresponding diones. The process of the invention thus enables the production of 2,2,4,4-tetraalkylcyclobutane-l,3-diols with an optimum cis-trans ratio regardless of the hydrogenation catalyst used.

[0008] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about." Unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, each numerical parameter should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Further, the ranges stated in this disclosure and the claims are intended to include the entire range specifically and not just the endpoint(s). For example, a range stated to be 0 to 10 is intended to disclose all whole numbers between 0 and 10 such as, for example 1, 2, 3, 4, etc., all fractional numbers between 0 and 10, for example 1.5, 2.3, 4.57, 6.1113, etc., and the endpoints 0 and 10. Also, a range associated with chemical substituent groups such as, for example, "CI to C5 hydrocarbons", is intended to specifically include and disclose CI and C5 hydrocarbons as well as C2, C3, and C4 hydrocarbons.

[0009] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as prec/ ^' sely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in its respective testing measurements.

[0010] Also, it is to be understood that the mention of one or more process steps does not preclude the presence of additional process steps before or after the combined recited steps or intervening process steps between those steps expressly identified. Moreover, the lettering of process steps or ingredients is a convenient means for identifying discrete activities or ingredients and the recited lettering can be arranged in any sequence, unless otherwise indicated.

[0011] As used herein, the terms "tetraalkylcyclobutanediol" and "tetramethyl- cyclobutanediol" are understood to be synonymous with the terms "2,2,4,4- tetraalkylcyclobutane-l,3-diol" and "2,2,4,4-tetramethylcyclobutane-l,3-diol" respectively. The term "starting 2,2,4,4-tetraalkylcyclobutane-l,3-diol" or "starting 2,2,4,4- tetramethylcyclobutane-l,3-diol" is intended to mean a 2,2,4,4-tetraalkylcyclobutane-l,3- diol or 2,2,4,4-tetramethylcyclobutane-l,3-diol that is used as a reactant in the process of the invention, i.e., a tetraalkylcyclobutanediol or 2,2,4,4-tetramethylcyclobutane-l,3-diol that has not been isomerized by the process of the invention. By contrast, the term

"isomerized 2,2,4,4-tetraalkylcyclobutane-l,3-diol" or "isomerized 2,2,4,4- tetramethylcyclobutane-l,3-diol," as used herein, is understood to mean a 2,2,4,4- tetraalkylcyclobutane-l,3-diol or 2,2,4,4-tetramethylcyclobutane-l,3-diol that has been subjected to and isomerized by the process of the invention.

[0012] Our process provides a process for isomerizing a 2,2,4,4-tetraalkylcyclobutane-l,3- diol having the formula (II):

II

wherein the R groups are identical, alkyl radicals having 1 to 8 carbon atoms. For example, the alkyl radicals represented by R can comprise 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 2 carbon atoms. The alkyl radicals may be linear or branched. Representative alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, and octyl. Some examples of 2,2,4,4- tetralkylcyclobutane-l,3-diols that can be used in the process of the invention include 2,2,4,4-tetramethylcyclobutane-l,3- diol, 2,2,4,4-tetraethylcyclobutane-l,3-diol, 2,2,4,4- tetra-n-propylcyclobutane-l,3-diol, 2,2,4,4-tetra-n-butylcyclobutane-l,3-diol, 2,2,4,4-tetra-n-amylcyclobutane- 1,3-diol, 2,2,4,4- tetraisobutylcyclobutane-l,3-diol, 2,2,4,4-tetra-n-hexylcyclobutane-l,3-diol, 2,2,4,4-tetra-n- heptylcyclobutane-l,3-diol, and 2,2,4,4-tetra-n-octylcyclobutane-l,3-diol. Our invention can be further described and illustrated herein with particular reference to 2,2,4,4- tetramethylcyclobutane-l,3-diol in which R is a methyl radical. It is understood that the embodiments described for 2,2,4,4-tetramethylcyclobutane-l,3-diol also apply to the other 2,2,4,4-tetraalkylcyclobutane-l,3-diols described hereinabove.

[0013] Tetraalkylcyclobutanediols typically are produced by hydrogenation of the corresponding tetraalkylcyclobutanediones using a variety of metal catalysts such as, for example, those catalysts containing nickel, ruthenium, and cobalt. For example, the hydrogenation of 2,2,4,4-tetramethylcyclobutane-l,3-dione to 2,2,4,4- tetramethylcyclobutane-l,3-diol can be carried out using nickel- or ruthenium-containing catalysts as described in U.S. Patents No.'s 3,000,906, 3,190,928; 5,169,994; 5,258,556; and 2,936,324. Cobalt-containing catalysts also may be used. For example, U.S. Patent No.'s 5,528,556 and 5,169,994 disclose the use of Raney cobalt for hydrogenation of 2,2,4,4- tetramethylcyclobutane-l,3-dione to 2,2,4,4-tetramethylcyclobutane-l,3-diol. In one embodiment of our process, for example, the starting 2,2,4,4-tetraalkylcyclobutane-l,3-diol is produced by hydrogenation of 2,2,4,4-tetramethylcyclobutane-l,3-dione.

[0014] The starting tetralkylcyclobutanediol can be used as a mixture of cis and trans isomers or as purified cis or trans isomers. For example, 2,2,4,4-tetramethylcyclobutane-l,3- diol may be used as pure cis or trans isomers, or as a mixture of cis and trans isomers. In one embodiment of our invention, the starting 2,2,4,4-tetraalkylcyclobutane-l,3-diol can have a cis:trans molar ratio of about 0:1 to about 1.5:1. Persons of skill in the art will understand that a cis:trans ratio of 0:1 is the equivalent of having the pure trans isomer. Some other representative examples of ranges of cis:trans ratios of the starting 2,2,4,4- tetraalkylcyclobutane-l,3-diol are 0.2: 1 to about 0.4:1, about 0.2:1 to about 0.7:1, about 0.2:1 to about 1:1, and about 0.2:1 to about 1.2:1. In one example, the starting 2,2,4,4- tetraalkylcyclobutane-l,3-diol can comprise a substantially pure trans-2,2,4,4- tetraalkylcyclobutane-l,3-diol, that is, a 2,2,4,4-tetraalkylcyclobutane-l,3-diol comprising about 95 mole percent or greater of the trans isomer.

[0015] The starting 2,2,4,4-tetraalkylcyclobutane-l,3-diol is contacted with hydrogen in the presence of a supported ruthenium catalyst. The source and purity of the hydrogen gas are not critical, and the hydrogen gas may comprise fresh hydrogen or a mixture of fresh hydrogen and recycled hydrogen. For example, hydrogen can be a mixture of hydrogen, optionally minor amounts, typically less than about 30 mole %, of components such as CO and C0 ₂ , and inert gases, such as argon, nitrogen, or methane. Typically, the hydrogen gas comprises at least about 70 mole % of hydrogen. For example, the hydrogen gas can comprise at least 90 mole % or, in another example, at least 97 mole %, of hydrogen. The hydrogen gas can be obtained from any of the conventional sources well known in the art such as, for example, by partial oxidation or steam reforming of natural gas. Pressure swing absorption can be used if a high purity hydrogen gas is desired. If hydrogen gas recycle is utilized in the isomerization process, then the recycled hydrogen gas may contain minor amounts of one or more products of the isomerization reaction which have not been fully condensed in the product recovery stage downstream from the isomerization reaction.

[0016] The temperature and hydrogen pressure used in the isomerization process of the invention can also be varied over a wide range depending on the activity of the catalyst, the mode of operation, and the desired rate of conversion. Typically, the process can be carried out under elevated hydrogen pressures of up to about 50.66 MPa (megapascals) and at temperatures of about 75° C to about 250° C. Some additional, more specific ranges of hydrogen pressures are about 0.3 to about 35 MPa, about 0.3 to about 5.2 MPa, about 0.3 to about 3.5 MPa, and about 0.4 to about 2.8 MPa. Some additional temperature ranges for the isomerization reaction are about 100 to about 200 °C and about 100 to about 175 °C. Persons of having ordinary skill in the art will recognize that any combination of the above temperatures and pressures can be used. In one embodiment of the invention, for example, the isomerization process can be carried at a temperature of about 100 to about 200°C and a hydrogen pressure of about 0.4 to about 2.8 megapascals.

[0017] The catalyst of the present invention comprises ruthenium deposited on a catalyst support. The term "support," as used in the context of the present specification and claims is intended to have its commonly accepted meaning as would be well-understood by persons of ordinary skill in the art, that is, a nominally inert material on which a catalytically active material, e.g., typically a metal, is deposited. The term, "deposited on," as used herein, is understood to mean any known method for adding the metal to the support including, but not limited to, depositing, adsorption, impregnation, ion-exchange, admixing, coprecipitation, and the like.

[0018] The ruthenium may be deposited on any recognized support material. For example, the support may comprise materials such as chromia, rare earth metal oxides, mixed metal oxides, zinc oxide, alumina, silica, silica-alumina, silicon carbide, zirconia, titania, activated carbon, graphite, graphitized carbon, carbon nano-tubes, zeolites, or mixtures thereof. These support materials are well-known to persons skilled in the art. For example, graphitized carbon supports are described in Rossetti et al. Catalysis Today, 2005, 102-103, pp. 219-224, and in U.S. Patent No. 7,115,239. The catalyst support may be further compounded with one or more binders to aid in pellet formation.The catalyst support along with any binder can be fabricated in any of the commonly used forms well-known in the art such as, for example, powders, extrudates, chips, granules, monoliths, pellets, cylinders, rings, saddles, spheres, stars, single lobe or multiple-lobe shapes, and the like. Depending on the particular support material employed and/or the method used to prepare a catalyst, ruthenium may be deposited primarily on the surface of the support or distributed throughout the support.

[0019] In one embodiment, the catalyst comprises ruthenium supported on carbon nanotubes. Carbon nanotubes (also known as fibrils) are well-known in the art as vermicular carbon deposits having diameters less than 1.0 μιη. Some additional examples of carbon nanotube diameters are less than 0.5 μιη and less than 0.2 μιη. Carbon nanotubes can be either multi walled (i.e., have more than one graphene layer more or less parallel to the nanotube axis) or single walled (i.e., have only a single graphene layer parallel to the nanotube axis). Other types of carbon nanotubes are also known, such as fishbone fibrils (e.g., wherein the graphene sheets are disposed in a herringbone pattern with respect to the nanotube axis), etc. As produced, carbon nanotubes may be in the form of discrete nanotubes, aggregates of nanotubes (i.e., dense, microscopic particulate structures comprising entangled carbon nanotubes) or a mixture of both. Some representative examples of carbon nanotubes are described in U.S. Patent Application Publication No.'s 2009 0208391; 2008 0176069; 2008 0175787; 2006 0239893; 2006 0142149; 2006 0142148; and 2003 0039604.

[0020] The catalyst can have a wide range of ruthenium content. Typically, the total amount of ruthenium present may be about 0.1 to about 10 weight percent based on the total weight of the catalyst. Some additional examples of ruthenium content are about 0.1 to about 9 weight percent, and about 0.2 to about 7 weight percent. For example, the catalyst can comprise about 1 to about 9 weight percent ruthenium deposited on a support comprising activated carbon, carbon nanotubes, silica, alumina, or a mixture thereof. [0021] The catalyst may be prepared by conventional techniques such as, for example, vapor deposition or impregnation of ruthenium onto the support material. Ruthenium may be provided as the metal itself or in the form of well-known ruthenium compounds such as, for example, ruthenium salts of inorganic or organic acids, ruthenium oxides, and

organometallic complexes containing ruthenium. The support material may be impregnated with ruthenium metal by immersing the support material in a solution of a ruthenium compound in a suitable solvent or by spraying the support material with the solution. The support material typically is dried and the catalyst exposed to a reducing environment, e.g., hydrogen, in order to reduce the ruthenium compounds to ruthenium metal.

[0022] Our isomerization process produces an isomerized 2,2,4,4-tetraalkylcyclobutane- 1,3-diol having a different ratio of cis to trans isomers than the starting 2,2,4,4- tetraalkylcyclobutane-l,3-diol. For example, the starting tetraalkylcyclobutanediol can have a cis:trans isomer ratio of about 0:1 to about 1.5:1 and the isomerized tetraalkylcyclobutanediol can have a cis:trans molar ratio of greater than 1:1 to about 2:1. In another example, the starting tetraalkylcyclobutanediol can be 2,2,4,4-tetramethylcyclobutane-l,3- diol having a cis:trans isomer ratio of about 0:1 to less than 1:1 and produces an isomerized 2,2,4,4-tetramethylcyclobutane-l,3-diol with a cis:trans molar ratio of greater than 1:1 to about 2:1. In yet another example, the starting tetraalkylcyclobutanediol is a trans-2,2,4,4- tetramethylcyclobutane-l,3-diol (cis:trans ratio of 0) and produces an isomerized 2,2,4,4- tetramethylcyclobutane-l,3-diol with a cis:trans ratio of about 0.3:1 to about 1.5:1. In yet another example, the starting tetraalkylcyclobutanediol is a 2,2,4,4-tetramethylcyclobutane- 1,3-diol having a cis:trans ratio of about 0.1:1 to about 1:1 that produces an isomerized 2,2,4,4-tetramethylcyclobutane-l,3-diol having a cis:trans ratio of about 0.4:1 to about 1.5:1. Our process also can be used to isomerize c/ ^' s-tetraalkylcyclobutanediols to the trans isomers. For example, the starting tetraalkylcyclobutanediol can have a cis:trans isomer ratio of about 3:1 to about 20:1 to produce an isomerized tetraalkylcyclobutanediol having a cis:trans ratio of about 1.5:1 to about 5:1.

[0023] The process of the invention has no net production of 2,2,4,4-tetraalkyl- cyclobutane-l,3-diol. The phrase "no net production" is intended to mean that no 2,2,4,4- tetraalkylcyclobutane-l,3-diol in addition to that already present as the starting 2,2,4,4- tetraalkylcyclobutane-l,3-diol is generated over the course of the isomerization reaction. For example, 1 mole of a starting tetraalkylcyclobutanediol would be expected to produce about 1 mole or less (as a result of adventitious losses from handling, transfers, by-product formation, etc.) of isomerized tetraalkylcyclobutanediol. The present invention, therefore, would be distinguished from a process for the preparation of a tetraalkylcyclobutanediol by hydrogenation of the corresponding tetraalkylcyclobutanedione because there would be a net increase in the amount of tetraalkylcyclobutanediol over the course of the

hydrogenation process.

[0024] The isomerization process may be carried out using the neat tetraalkylcyclobutanediol or in the presence of a solvent that may be selected from a wide variety of compounds or mixture of compounds. The solvent can be any substance that is liquid under the operating conditions of the isomerization process, does not adversely affect the isomerization process, and is substantially inert or shows limited reactivity (e.g., typically less than 1% conversion under process conditions) with respect to the catalyst, hydrogen and tetraalkylcyclobutanediol. Some representative examples of solvents that may be used to dissolve the starting 2,2,4,4-tetraalkylcyclobutane-l,3-diol, include water, alcohols, ethers, glycols, glycol ethers, alkanes, esters, and mixtures thereof. Some specific examples of solvents that may used in the isomerization process include, but are not limited to, water, methanol, ethanol, propanol, 1-butanol, 2-butanol, 2-ethylhexanol, 2,2-dimethyl-l,3- propanediol, ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, hexane, heptane, cyclohexane, octane, decane, diethyl ether, diisopropyl ether, tetrahydrofuran, methyl tert-butyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethyl acetate, n-propyl acetate, isopropyl isobutyrate, isobutyl propionate, octyl acetate, isobutyl isobutyrate, isobutyl acetate, methyl butyrate, and mixtures thereof. In one embodiment, for example, the solvent comprises isobutyl isobutyrate. Typically, the 2,2,4,4-tetraalkylcyclobutane-l,3-diol can be dissolved in the solvent at a concentration of about 1 to about 60 weight percent, based on the total weight of the

tetraalkylcyclobutanediol solution. Some other examples of tetraalkylcyclobutanediol concentrations are about 5 to about 50 weight percent and about 10 to about 25 weight percent. In another example, the tetraalkylcyclobutanediol comprises trans-2,2,4,4- tetraalkylcyclobutanediol and is dissolved in a solvent comprising isobutyl isobutyrate at a concentration of about 1 to about 60 weight percent, about 5 to about 50 weight percent, or about 10 to about 25 weight percent.

[0025] The isomerization process can be carried out as a batch, semi-continuous or continuous process, and may utilize a variety of reactor types. Some examples of suitable reactor types include stirred tank, continuous stirred tank, slurry, tubular, fixed bed, and trickle bed. The term "continuous," as used herein, means a process wherein reactants are introduced and products withdrawn simultaneously in an uninterrupted manner. By "continuous" it is meant that the process is substantially or completely continuous in operation in contrast to a "batch" process. The term "batch" process as used herein means a process wherein all the reactants are added to the reactor and then processed according to a predetermined course of reaction during which no material is fed or removed into the reactor. For example, in a batch operation, a slurry of the catalyst in the

tetraalkylcyclobutanediol and/or a solvent in which the tetraalkylcyclobutanediol has been dissolved is fed to a pressure vessel equipped with means for agitation. The pressure vessel is then pressurized with hydrogen to a predetermined pressure followed by heating the reaction mixture to the desired temperature. After the reaction is complete, the reaction mixture is removed from the pressure vessel, the catalyst is separated by filtration, and the isomerized tetraalkylcyclobutanediol is isolated, for example, by distillation or by

crystallization. The term "semicontinuous" means a process in which some of the reactants are charged at the beginning of the process and the remaining reactants are fed

continuously as the reaction progresses. Alternatively, a semicontinuous process also may include a process similar to a batch process in which all the reactants are added at the beginning of the process except that one or more of the products are removed continuously as the reaction progresses.

[0026] For economic and operability reasons, the process is advantageously operated as a continuous process. Continuous operation may utilize a fixed bed with a larger particle size of catalyst such as, for example, granules, pellets, various multilobal shaped pellets, rings, or saddles that are well known to skilled persons in the art. As an example of a continuous process, a high pressure, tubular or columnar reactor utilizing a fixed catalyst bed may be used in which the liquid tetraalkylcyclobutanediol, with or without a solvent, can be fed continuously into the top of the bed at elevated pressure and temperature. The crude isomerization product can be removed from the base of the reactor. Alternatively, it is possible to feed the tetraalkylcyclobutanediol into the bottom of the bed and remove the isomerized product from the top of the reactor. It is also possible to use 2 or more catalyst beds connected in parallel or in series to improve conversion, to reduce the quantity of catalyst, or to bypass a catalyst bed for periodic maintenance or catalyst removal. Another mode of continuous operation utilizes a slurry of the catalyst in an agitated pressure vessel that is equipped with a filter leg to permit continuous removal of a solution of the isomerized product in the tetraalkylcyclobutanediol and/or a solvent. In this manner a liquid, starting tetraalkylcyclobutanediol or solution thereof can be continuously fed to and the product or product solution continuously removed from an agitated pressure vessel containing a slurry of the catalyst.

[0027] In one embodiment, for example, a starting 2,2,4,4-tetramethylcyclobutane-l,3- diol, a solvent, and hydrogen can be contacted continuously with a catalyst comprising ruthenium deposited on a support material in an isomerization zone at a hydrogen pressure of about 0.7 MPa to about 6.9 MPa and a temperature of about 75 to about 250° C. This embodiment can include continuously recovering an effluent from the isomerization zone comprising the solvent and an isomerized 2,2,4,4-tetramethylcyclobutane-l,3-diol having a cis:trans ratio different from that of the starting 2,2,4,4-tetramethylcyclobutane-l,3-diol. In another embodiment, the process may further comprise continuously recycling a portion of the product effluent to the isomerization zone. The isomerization zone may be any suitable reactor type including, but are not limited to, stirred tank, continuous stirred tank, slurry, tubular, fixed bed, and trickle bed. For example, the process of the invention may be carried out in a trickle bed reactor operated in the liquid phase.

[0028] The process may be conducted in the liquid phase, the vapor phase, or a combination of liquid and vapor phases. For example, the process may be carried in the vapor phase in a similar manner as the hydrogenation processes disclosed in U.S. Patent No. 5,395,987. As a vapor phase process, our isomerization process can be operated using vaporous feed conditions by feeding the tetraalkylcyclobutanediol in essentially liquid free, vaporous form to an isomerization zone comprising the supported ruthenium catalyst. Hence, the feed stream is introduced into the isomerization zone at a temperature which is above the dew point of the mixture. The term "dew point", as used herein, means that temperature at which a gas or a mixture of gases is saturated with respect to a condensable component. Typically the feed temperature of the vaporous feed mixture to the

isomerization zone is from about 5 °C to about 10 °C or more above its dew point at the operating pressure.

[0029] A convenient method of forming a vaporous mixture is to spray liquid

tetraalkylcyclobutanediol or a tetraalkylcyclobutanediol solution into a stream of hot hydrogen-containing gas to form a saturated or partially saturated vaporous mixture.

Alternatively, such a vapor mixture can be obtained by bubbling a hot hydrogen-containing gas through a body of the liquid tetraalkylcyclobutanediol or tetraalkylcyclobutanediol solution. If a saturated vapor mixture is formed it should then be heated further or diluted with more hot gas to produce a partially saturated vaporous mixture prior to contact with the catalyst. To maintain the vaporous feed stream above its dew point at the inlet end of a catalyst bed at the operating pressure, the hydrogen-containing gas:

tetraalkylcyclobutanediol molar ratio is desirably about 10:1 to about 8000:1 or, in another example, about 200:1 to about 1000:1.

[0030] The process of the invention can be used to isomerize trans-2,2,4,4- tetramethylcyclobutane-l,3-diol to a c/ ^' s-2,2,4,4-tetramethylcyclobutane-l,3-diol or a mixture of cis- and trans-2,2,4,4-tetramethylcyclobutane-l,3-diols. Thus, another aspect of our invention is process for the isomerization of a 2,2,4,4-tetraalkylcyclobutane-l,3-diol, comprising contacting trans-2,2,4,4-tetramethylcyclobutane-l,3-diol with a catalyst comprising about 1 to about 9 weight percent ruthenium, based on the total weight of the catalyst, deposited on a support comprising silica, alumina, silica-alumina, titania, zirconia, activated carbon, graphitized carbon, carbon nanotubes, zeolites, chromia, rare earth metal oxides, or mixtures thereof at a pressure of about 0.4 to about 3.5 mega pascals and a temperature of about 100 to about 250°C to form c/ ^' s-2,2,4,4-tetramethylcyclobutane-l,3- diol, wherein the process has no net production of 2,2,4,4-tetraalkylcyclobutane-l,3-diol. It is understood that the above process encompasses the various embodiments of the cisitrans isomer ratios, catalyst support, reaction conditions of temperature and pressure, reactor formats, catalyst loadings, and solvents described hereinabove.

[0031] For example, the trans-2,2,4,4-tetramethylcyclobutane-l,3-diol can be dissolved in at least one solvent selected from water, alcohols, ethers, glycols, glycol ethers, alkanes, and esters. Some specific examples of solvents include water, methanol, ethanol, propanol, 1- butanol, 2-butanol, 2-ethylhexanol, 2,2-dimethyl-l,3-propanediol, ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, hexane, heptane, cyclohexane, octane, decane, diethyl ether, diisopropyl ether, tetrahydrofuran, methyl tert-butyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethyl acetate, n-propyl acetate, isopropyl isobutyrate, isobutyl propionate, octyl acetate, isobutyl isobutyrate, methyl butyrate, isobutyl acetate, and mixtures thereof. In another example, the support can comprise alumina, activated carbon, graphitized carbon, silica, silica-alumina, or carbon nanotubes.

[0032] The process of the invention also can be used to isomerize a 2,2,4,4- tetraalkylcyclobutane-l,3-diol having a high cis:trans ratios. Another embodiment of our invention, therefore, is a process for the isomerization of a 2,2,4,4-tetraalkylcyclobutane- 1,3-diol, comprising contacting a starting 2,2,4,4-tetraalkylcyclobutane-l,3-diol having a molar ratio of cis to trans isomers of 3:1 to about 20:1 with hydrogen in the presence of a catalyst comprising about 0.1 to about 10 weight percent ruthenium, based on the total weight of the catalyst, deposited on a support, to produce an isomerized 2,2,4,4- tetraalkylcyclobutane-l,3-diol having a ratio of cis to trans isomers of about 1.5:1 to about 5 :1, wherein the process has no net production of 2,2,4,4-tetraalkylcyclobutane-l,3-diol. It will be apparent to persons skilled in the art that the above process encompasses the various embodiments of the cis:trans isomer ratios, catalyst support, reaction conditions of temperature and pressure, reactor formats, catalyst loadings, and solvents that have been described previously. For example, the above process can be in operated as a continuous process and can employ a solvent to dissolve the starting tetramethylcyclobutanediol. As noted above, the solvent can include one or more of water, methanol, ethanol, propanol, 1- butanol, 2-butanol, 2-ethylhexanol, 2,2-dimethyl-l,3-propanediol, ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, hexane, heptane, cyclohexane, octane, decane, diethyl ether, diisopropyl ether, tetrahydrofuran, methyl tert-butyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethyl acetate, n-propyl acetate, isopropyl isobutyrate, isobutyl propionate, octyl acetate, isobutyl isobutyrate, isobutyl acetate methyl butyrate, or mixtures thereof at a concentration of about 10 to about 25 weight percent, based on the total weight of the solution.

[0033] The invention also includes the following embodiments that are set forth below and in paragraphs [0034]-[0043]: a process for the isomerization of a 2,2,4,4- tetraalkylcyclobutane-l,3-diol, comprising contacting a starting 2,2,4,4-tetraalkyl- cyclobutane-l,3-diol having a ratio of cis to trans isomers of about 0:1 to about 1.5:1 with hydrogen in the presence of a catalyst comprising about 0.1 to about 10 weight percent ruthenium, based on the total weight of the catalyst, deposited on a support, to produce an isomerized 2,2,4,4-tetraalkylcyclobutane-l,3-diol having a different ratio of cis to trans isomers than the starting 2,2,4,4-tetraalkylcyclobutane-l,3-diol, in which the process has no net production of 2,2,4,4-tetraalkylcyclobutane-l,3-diol.

[0034] A process that includes the embodiments of paragraph [0033], wherein the starting 2,2,4,4-tetraalkylcyclobutane-l,3-diol has the general formula (II):

(II)

wherein R is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl; and the support comprises silica, alumina, silica-alumina, titania, zirconia, activated carbon, graphite, graphitized carbon, carbon nanotubes, zeolites, chromia, rare earth metal oxides, or mixtures thereof.

[0035] A process that includes the embodiments of paragraph [0033] or [0034] wherein R is methyl.

[0036] A process that includes the embodiments of any one of paragraphs [0033]-[0035], wherein the starting 2,2,4,4-tetraalkylcyclobutane-l,3-diol has a cis:trans molar ratio of about 0:1 to less than 1:1 and the isomerized 2,2,4,4-tetraalkylcyclobutane-l,3-diol has a cis:trans molar ratio of greater than 1:1 to about 2:1.

[0037] A process that includes the embodiments of any one of paragraphs [0033]-[0036], wherein the catalyst comprises about 1 to about 9 weight percent ruthenium and the support comprises activated carbon, graphitized carbon, carbon nanotubes, silica, alumina, or a mixture thereof.

[0038] A process that includes the embodiments of any one of paragraphs [0033]-[0037], which is at a temperature of about 100 to about 200°C and a hydrogen pressure of about 0.4 to about 2.8 megapascals.

[0039] A process that includes the embodiments of any one of paragraphs [0033]-[0038], wherein the starting 2,2,4,4-tetraalkylcyclobutane-l,3-diol is dissolved in at least one solvent selected from water, alcohols, ethers, glycols, glycol ethers, alkanes, and esters.

[0040] A process that includes the embodiments of any one of paragraphs [0033]-[0039], wherein the solvent is selected from water, methanol, ethanol, propanol, 1-butanol, 2- butanol, 2-ethylhexanol, 2,2-dimethyl-l,3-propanediol, ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, hexane, heptane, cyclohexane, octane, decane, diethyl ether, diisopropyl ether, tetrahydrofuran, methyl tert-butyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethyl acetate, n-propyl acetate, isopropyl isobutyrate, isobutyl propionate, octyl acetate, isobutyl isobutyrate, isobutyl acetate, methyl butyrate, and mixtures thereof.

[0041] A process that includes the embodiments of any one of paragraphs [0033]-[0040], which is a continuous process.

[0042] A process that includes the embodiments of any one of paragraphs [0033]-[0041], wherein the process is conducted in the liquid phase, vapor phase, or a combination of liquid and vapor phase.

[0043] A process that includes the embodiments of any one of paragraphs [0033]-[0042], wherein the starting 2,2,4,4-tetraalkylcyclobutane-l,3-diol is produced by hydrogenation of 2,2,4,4-tetramethylcyclobutane-l,3-dione.

[0044] The process of the invention are further described and illustrated by the following examples. EXAMPLES

[0045] The invention is further illustrated by the following examples. All percentages are by weight unless specified otherwise. The carbon nanotube support material used in the examples was 1.6 mm (1/16 inch) extrudates obtained from Hyperion Catalyst International, Inc. Catalyst surface areas were measured volumetrically using the Brunauer-Emmett-Teller (BET) method. Analysis of reaction products was performed by gas chromatography using a DB™-Wax column (30 meters x 0.25 mm ID, 0.5 micron film thickness) over a temperature range of 50 to 240 °C and a flame ionization detector. The reaction samples were dissolved in dimethyl sulfoxide before injection into the gas chromatograph. Trace amounts (e.g., typically less than 0.1 weight percent) of 2,2,4-trimethyl-l,3-pentanediol, 2,4-dimethyl-3- pentanol (diisopropyl carbinol), 2,2,4-trimethyl-3-pentanol, 2,2,4-trimethyl-l-pentanol, 2,2,4-trimethyl-3-oxo-l-pentanol, and 2,2,4,4-cyclobutaneketol also were detected by GC in the Examples unless indicated otherwise. All pressures are reported as gauge unless indicated otherwise.

[0046] Example 1 - A pre-reduced catalyst (2 g) containing 7 weight percent Ru on a graphitized carbon support (purchased from BASF Catalysts under the designation "C3610") and having a surface area of 589 m ² /g was loaded in a 100 mL stainless steel autoclave with 6 g of trans-2,2,4,4-tetramethylcyclobutane-l,3-diol and 54 g of isobutyl isobutyrate (IBIB). The autoclave was agitated and purged twice with 0.7 MPa (100 psig) helium at ambient temperature and then purged with 0.7 MPa (100 psig) hydrogen. The autoclave was heated to 100 °C and pressurized to 1.4 MPa (200 psig) with hydrogen. After 2 hours, a product sample was taken and analyzed by gas chromatograph (GC). The conversion of trans-2,2,4,4- tetramethylcyclobutane-l,3-diol was 55% and the ratio of cis to trans isomers was 1.2:1.

[0047] Example 2 - The same catalyst in Example 1 (0.9 g) was loaded in a 100 mL stainless steel autoclave reactor with 7 g of trans-2,2,4,4-tetramethylcyclobutane-l,3-diol and 63 g of isobutyl isobutyrate. The autoclave was agitated and purged twice with helium (0.7 MPa, 100 psig) at ambient temperature and then purged with hydrogen (0.7 MPa, 100 psig). The autoclave was heated to 120 °C and pressurized to 1.4 MPa (200 psig) with hydrogen. After 3 hours, a product sample was taken and analyzed. The conversion of trans- 2,2,4,4-tetramethylcyclobutane-l,3-diol was 46% and the ratio of cis to trans isomers was 0.85:1.

[0048] Example 3 -A mixture of 6 g of tra/is-2,2,4,4-tetramethylcyclobutane-l,3-diol, 54 g of IBIB, and 2 grams of a 2 weight percent Ru on silica catalyst (surface area = 300 m ² /g, obtained from BASF Catalysts) was loaded in a 100 mL stainless steel autoclave reactor. The autoclave was agitated and purged twice with helium (0.7 MPa, 100 psig) at an ambient temperature and purged with hydrogen at a pressure of 0.7 MPa (100 psig). The autoclave was then heated to 110 °C and pressurized to 1.4 MPa (200 psig) with hydrogen. After 2 hours, a product sample was taken and analyzed by GC. The conversion of trans-2,2,4,4- tetramethylcyclobutane-l,3-diol was 32% and the ratio of cis to trans isomers was 0.47:1.

[0049] Example 4 - A mixture of 6 g of trans-2,2,4,4-tetramethylcyclobutane-l,3-diol, 54 g of IBIB, and 2 grams of a 2 weight percent Ru on a-alumina catalyst (surface area = 40 m ² /g, obtained from BASF Catalysts) was loaded in a 100 mL stainless steel autoclave. The autoclave was agitated and purged twice with helium at a pressure of 0.7 MPa (100 psig) at ambient temperature and with hydrogen at a pressure of 0.7 MPa (100 psig). The autoclave was then heated to 110 °C and pressurized to 1.4 MPa (200 psig) with hydrogen. After 2 hours, a product sample was taken and analyzed by GC. The conversion of trans-2,2,4,4- tetramethylcyclobutane-l,3-diol was 35% and the ratio of cis to trans isomers was 0.55:1.

[0050] Example 5 - The same catalyst in Example 1 (0.9 g) was loaded in a 100 mL stainless steel autoclave reactor with 7 g of trans-2,2,4,4-tetramethylcyclobutane-l,3-diol and 63 g of IBIB. The autoclave was agitated and purged twice with helium at a pressure of 0.7 MPa (100 psig) at ambient temperature and with hydrogen at a pressure of 0.7 MPa (100 psig). The autoclave was heated to 120 °C and pressurized to 2.1 MPa (300 psig) with hydrogen. After 4 hours, a product sample was taken and analyzed by GC. The conversion of trans-2,2,4,4-tetramethylcyclobutane-l,3-diol was 54% and the ratio of cis to trans isomers was 1.16:1.

[0051] Comparative Example 1: Isomerization in the absence of hydrogen and catalyst - rrans-2,2,4,4-tetramethylcyclobutane-l,3-diol (6 g) and 54 g of isobutyl isobutyrate were added to a 100 mL stainless steel autoclave reactor. The autoclave was agitated and purged twice with helium a pressure of 0.7 MPa (100 psig) at ambient temperature. The autoclave was then heated to 150 °C. After 4 hours, a product sample was taken and analyzed by GC. The conversion of trans-2,2,4,4-tetramethylcyclobutane-l,3-diol was 1.6% and the ratio of cis to trans isomers was 0.016:1.

[0052] Comparative Example 2 - A mixture of 65 g IBIB and 2 g of 5 weight percent Pd on alumina powder (surface area = 88 m ² /g, obtained from Engelhard, now BASF Catalysts) was loaded in a 100 mL stainless steel autoclave. The autoclave was agitated and purged twice with helium (0.7 MPa, 100 psig) and then hydrogen at pressure of 0.7 MPa (100 psig) at ambient temperature. The autoclave was heated to 150 °C and the reactor pressure was increased to 2.8 MPa (400 psig) with hydrogen. After the 1 hour catalyst reduction, the reactor was cooled to approximately 50 °C and 3.5 g of trans- 2,2,4,4- tetramethylcyclobutane-l,3-diol was added to the autoclave. The autoclave was agitated and purged twice with helium (0.7 MPa, 100 psig) followed by hydrogen (0.7 MPa, 100 psig). The autoclave was then heated to 200 °C and pressurized to 2.8 MPa (400 psig). After 3 hours, GC analysis of the reaction mixture show the cis- and trans-2,2,4,4- tetramethylcyclobutane-l,3-diol concentrations to be 0.042 and 5.24 weight percent, respectively. Because the conversion to the cis isomer was low, the concentration of the trans-2,2,4,4-tetramethylcyclobutane-l,3-diol isomer in the product mixture was higher than in the starting mixture, presumably as the result of an error in the GC analysis. The conversion of the ίτα/is-isomer was 0.84 % and the ratio of the cis to trans isomers was 0.008. This conversion was based on the ratio of the cis isomer to the total amount of 2,2,4,4-tetramethylcyclobutane-l,3-diol in the product mixture.

[0053] Comparative Example 3 - A S weight percent Pt on activated carbon powder catalyst (2.97 g, surface area = 607 m ² /g, obtained from Engelhard, now BASF Catalysts) was dried overnight in a conventional oven at 105 °C and charged to a 100 mL stainless steel autoclave. The autoclave was purged twice with helium (0.7 MPa, 100 psig) and then hydrogen (0.7 MPa, 100 psig) at ambient temperature. The autoclave was heated to 150 °C and the reactor pressure was increased to 2.8 MPa (400 psig) with hydrogen. After the 1 hour, the autoclave was cooled to approximately 50 °C and 66.5 g of isobutyl isobutyrate (IBIB) and 3.5 g of trans-2,2,4,4-tetramethylcyclobutane-l,3-diol were added. The autoclave was agitated and purged twice with helium (0.7 MPa, 100 psig) followed by hydrogen (0.7 MPa, 100 psig). The autoclave was then heated to 200 °C and pressurized to 2.8 MPa (400 psig). After 3 hours, GC analysis of the reaction mixture show the cis- and trans-2,2,4,4- tetramethylcyclobutane-l,3-diol concentrations to be 0.043 and 3.93 weight percent, respectively. The conversion of the trans-d\o\ was 21% and the ratio of cis to trans isomers was 0.01. Significant amount of by-products such as 2,2,4-trimethyl-l,3-pentanediol, 2,4- dimethyl-3-pentanol (diisopropyl carbinol), 2,2,4-trimethyl-3-pentanol, and 2,2,4-trimethyl- 1-pentanol was found in the final reaction mixture.

[0054] Comparative Example 4: Isomerization in the absence of hydrogen - The same catalyst in Example 1 (2 g) was loaded in a 100 mL stainless steel autoclave reactor with 6 g of trans-2,2,4,4-tetramethylcyclobutane-l,3-diol and 54 g of isobutyl isobutyrate. The autoclave was agitated and purged twice with helium 0.7 MPa (100 psig) at ambient temperature and then heated to 150 °C. After 4 hours, a product sample was taken and analyzed by GC. The conversion of tra/is-2,2,4,4-tetramethylcyclobutane-l,3-diol was 2.6% and the ratio of cis to trans isomers was 0.027:1.

[0055] Comparative Example 5: Isomerization with a supported Ni catalyst - Four grams of a Ni-3288 catalyst (purchased from BASF Catalysts) having a surface area of 160 m ² /g and containing 39 weight percent NiO, 31 weight percent Ni, 13 weight percent Bentonite clay, 13 weight percent alumina, 3 weight percent calcium silicate, and 0.1-1 weight percent crystalline silica), were placed in a 100 mL stainless steel autoclave reactor with 72 g of isobutyl isobutyrate. The autoclave was agitated and purged twice with helium a pressure of 0.7 MPa (100 psig) and then with hydrogen at pressure of 0.7 MPa (100 psig) at ambient temperature. The autoclave was heated to 150 °C, and the reactor pressure was increased to 2.8 MPa (400 psig) with hydrogen. After the 2 hours, the reactor was cooled

approximately 50 °C. Six grams of trans-2,2,4,4-tetramethylcyclobutane-l,3-diol were then added to the reactor. The autoclave was agitated and purged twice with helium a pressure of 0.7 MPa (100 psig) followed by hydrogen, also at a pressure of 0.7 MPa (100 psig). The autoclave was then heated to 150 °C and pressurized to 2.8 MPa (400 psig) with hydrogen. After 5 hours, a product sample was taken and analyzed by GC. The conversion of trans- 2,2,4,4-tetramethylcyclobutane-l,3-diol was 1.2% and the ratio of cis to trans isomers was 0.22:1. [0056] Example 6 - The same catalyst in Example 1 (0.9 g) was loaded in a 100 mL stainless steel autoclave reactor with eight grams of c/ ^' s-2,2,4,4-tetramethylcyclobutane-l,3-diol and 72 g of isobutyl isobutyrate. The autoclave was agitated and purged twice with helium a pressure of 0.7 MPa (100 psig) at ambient temperature and then purged with hydrogen a pressure of 0.7 MPa (100 psig). The autoclave was then heated to 120 °C and pressurized to 2.8 MPa (400 psig) with hydrogen. After 3 hours, a product sample was taken and analyzed by GC. The conversion of c/ ^' s-2,2,4,4-tetramethylcyclobutane-l,3-diol was 25% and the ratio of cis to trans isomers was 2.93:1.

[0057] Example 7 - A 300 mL stainless steel autoclave was charged with a mixture of 6 g 90% tra/is-2,2,4,4-tetramethylcyclobutane-l,3-diol, 144 g water and a catalyst basket loaded with 5 grams of 2 weight percent Ru on a-alumina catalyst (surface area = 10 m ² /g, obtained from BASF Catalysts). The autoclave was agitated and purged three times with nitrogen at 0.7 MPa (100 psig) then with hydrogen at 1.4 MPa (200 psig) at ambient temperature. The autoclave was then heated to 120 °C and pressurized to 3.5 MPa (500 psig) with hydrogen. Samples were taken from the autoclave at 1, 3, 5, 10, 20, 30, 60, 90 and 120 minutes intervals and analyzed by gas chromatography (GC). After 30 minutes, the ratio of cis to trans isomers was 1.8:1, remaining essentially the same for the final samples. Conversion of the trans isomer was 64.5% to products. 2,2,4-Trimethyl-l,3-pentanediol (0.5% relative to the cis and trans diols) was the only byproduct detectable by GC analysis in the final sample.

[0058] Example 8 - A 300 mL stainless steel autoclave was charged with a mixture of 6 g >98% c/ -2,2,4,4-tetramethylcyclobutane-l,3-diol, 144 g water and a catalyst basket loaded with 5 grams of 2 weight percent Ru on a-alumina catalyst (surface area = 10 m ² /g, obtained from BASF Catalysts). The autoclave was agitated and purged three times with nitrogen at 0.7 MPa (100 psig) then with hydrogen at 1.4 MPa (200 psig) at ambient temperature. The autoclave was then heated to 120 °C and pressurized to 3.5 MPa (500 psig) with hydrogen. Samples were taken from the autoclave at 1, 3, 5, 10, 20, 30, 60, 90 and 120 minutes intervals and analyzed by gas chromatography (GC). After 60 minutes, the ratio of cis to trans isomers was 1.8:1 (65% and 35% respectively, by GC analysis), remaining essentially the same for the final samples. No byproduct was detectable by GC analysis in the final sample.