Process for making 1,3-glycols from epoxides

Descriptive MEMORY

Background of the Invention

This invention describes the process of preparing 1,3-diols in general and, in particular, preparing 1,3-diols from an epoxide. In one embodiment of the invention the preparation of 1.5-propanediol from ethylene oxide is described.

Glycols are generally valuable chemicals with a wide variety of applications. These compounds are, for example, used as intermediate chemicals in the preparation of esters as well as in the synthesis of polyesters. In particular propanediol-1,3, also called propylene glycol-1,3 or trimethylene glycol, has been especially useful in some applications. 0 propanediol-1,3 is typically prepared by acid catalyzed hydration of the acrolein to form the hydracrylaldate which is subsequently hydrated to the corresponding glycol. 0 The high cost of acrolein and the relatively low yields obtained in these reactions have not led to cost-competitive commercial production processes for propanediol-1,3 with other commercially available cords which in many cases may replace propanediol-1,3.

The preparation of 1,3-glycols by hydroformylation of epoxides using phosphine-modified carbonyl locobalt complex catalysts is mentioned in US Pat. This patent shows in particular the preparation of 1.3-propanediol by hydroformylation of ethylene oxide using a tertiary phosphine modified carbonylocobalt component per mol of oxide. of ethylene. Although high yields (92%) of propanediol-1,3 produced in diethyl ether as a solvent were claimed, the catalyst concentrations used were extremely high, the amount of ethylene oxide charged was low and neither the reaction or reaction rates. Income in

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3-propanediol-1,3 were substantially lower in solvents other than diethyl ether.

U.S. Patent 5,687,981 also relates to a process for preparing propanediol-1,3. However, the process disclosed in said patent uses two separate steps. In the first step the ethylene oxide undergoes a hydroformylation reaction producing hydroxyethyl hydroxydioxane which is insoluble in the initial reaction solvent. Dioxane is separated from the initial reaction solvent and is then catalytically hydrogenated to yield trimethylene glycol. The patent generally discusses the possibility of using, as catalysts for the hydroformylation reaction, the transition metals in particular those of Group VIII of the Periodic Table, ie cobalt, iron, nickel, osmium and tertiary carbonyl phosphine complexes. cobalt and rhodium carbonyl. Examples of said patent are, however, limited to the use of the dicobalt octacarbonyl catalyst.

U.S. Patent 3,054,813 is directed to a process for preparing 3-hydroxyaldehydes or alpha aldehydes beta-unsaturated by reaction of epoxides with synthesis gas. Said patent indicates the use of carbonylocobalt catalyst for the hydroformylation of ethylene oxide, but the resulting product was acrolyel.

An article by Yokokatua et al. In the Bulletin of the Chemical Society of Dapan (vol. 37, page 677, 1964) presents an attempt to hydroformylate ethylene oxide and propylene oxide using carbonylocobalt as a catalyst. . In the case of ethylene oxide the product was overwhelmingly composed of acetaldeldo. Small amounts of acrolelna were formed. In the case of propylene oxide, under certain conditions reasonable yields of

3-hydroxybutyraldehyde, but the preparation of butanediol-1,3 is not mentioned.

X

Processes that prepare 1,3-glycols from epoxides using hydroformylation catalysts are likely to produce 3-hydroxyaldehydes as integral chemicals.

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They may be either in situ hydrogenated to 1,3-glycols or otherwise isolated (as in the form of the hydroxyalkyl dioxanes mentioned above), and then hydrogenated in a separate step. 3-Hydroxyaldehydes, such as hydroacrylaldehyde, are however unusually reactive species and are easily subjected to various side reactions. In a bibliographical review entitled Neui Synthesis With Carbon Monoxide, B. Cornils, Sprinqer Verlag, p. 151, 1980 claims that numerous attempts have been made to subject oxiranes (epoxides) to the hydrophor reaction | due to its high reactivity not only of the epoxides but also of the resulting hydroxyaldehydes, hydroformylation of epoxides generally leads to the formation of a mixture of products and thus to unsatisfactory yields.

Under the conditions of a hydroformylation reaction, an isomerization of ethylene oxide to acetaldehyde (which may be hydrogenated to ethanol) may occur. In addition, if hydroformylation of ethylene oxide in hydracrylaldehyde results, hydracrylaldehyde may be dehydrated to produce acrolein which may be hydrogenated to propanal or propanol, or hydracrylaldehyde may undergo condensation reactions (aldol) with other aldehyde molecules giving branched C6 aldehydes which may undergo dehydration and hydrogenation reactions. It is therefore highly desirable for a catalyst for the preparation of 1,3-propanediol from oxy. of ethylene is capable of rapidly hydrogenating hydracrylaldehyde in situ before undesirable side reactions may occur. Such a catalyst should also have the economic advantage of producing 1,3-propanediol in a single reactor without the need for a large and expensive device for isolating and then hydrogenating the aldehydes.

Thus there remains a need for an efficient process for preparing 1,3-glycols, especially from epoxides, which is commercially usable.

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-5Summary of the Invention

It has now been found that epoxides can be convex? 1,3-glycols by a carbonylation reaction using rhodium as a catalyst. Thus, the present invention provides a process for preparing 1,3-glycols of formula

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I

FL-C-CH-CH-R I ² II oo

K where R represents hydrogen, a monovalent aromatic or aliphatic group having from 1 to about 12 carbon atoms, or a divalent aliphatic group having from 4 to about 6 carbon atoms, which together with X forms a cyclic structure, and X represents hydrogen or, if R is divalent, a bond with R. The process comprises reacting an epoxide of formula.

Hf --- CH-R II

X where R and X have the above meaning, with CO and H₂in a solvent suitable for the reaction, said process characterized in that the reaction mixture contains (1) an epoxide of said structure in a concentration between about 0.1 and about 30% by weight; (2) rhodium at a molar concentration between 0.00001 and about 0.1 molar; (3) a phosphine with f? mule p_RlR₂R₃ iii where R4, R₂ and R3 are independently selected from the group consisting of aliphatic and aromatic hydrocarbon groups, the rhodium: phosphine molar ratio being from about 10: 1 to about 1:10; (4) water in an amount from about 0.00 to about 25% by weight, based on the weight of the reaction mixture; (5) 00; (6) H₂ and (7) an acid being

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the acid: phosphine molar ratio from about 10: 1 to about 1:10; being the molar ratio C0: H₂ from about 10: 1 to about 1:10, and carrying out the reaction at a temperature of about 50 to about 2009 ° C, under a pressure of about 200 to about 10,000 psig, for a period of time. sufficient to form at least some desired 1,3-glycol.

Detailed Description of Preferred Embodiments of the Invention

As indicated above, the present invention provides a process for preparing 1,3 glycols by carbonylation of epoxides. The desired glycols therefore contain one more carbon atom and one more oxygen atom than the epoxide moiety. Thus, for example, when the epoxide is oxy. of ethylene, containing 2 carbon atoms, the resulting 1,3-glycol will be 1,3-propanediol containing 3 carbon atoms. Examples of other specific epoxides useful in the present invention are propylene oxide, 1,2-epoxyoctane, cyclohexene oxide and styrene oxide.

The epoxides, as indicated above, have the general formula

Where R is hydrogen, a monovalent aromatic or aliphatic group having from 1 to about 12 carbon atoms or a divalent aliphatic group having from 4 to about 6 carbon atoms, which together with X forms a cyclic structure and X represents hydrogen or, if R is divalent, a bond with R. R may therefore be a monovalent alkyl group having for example from 1 to 6 carbon atoms or may be a divalent alkyl group or an aromatic group, for example a phenyl group. If, for example, R is a divalent alkyl group of 4 carbon atoms then the epoxide will be cyclohexene oxide. Commonly epoxide is present in mis.

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Reaction time at a concentration of from about 0.1 to about 30% by weight. The concentration of epoxide is typically from about 1 to about 20% by weight.

Different epoxides may require different reaction conditions in order to obtain optimum results in terms of yield and selectivity as well as different specific components: rhodium, phosphine or acid. Using the rhodium system, tricyclohexylphosphine and phosphoric acid, ethylene oxide gives good yield of pro. and selectivity, and propylene oxide will give good product selectivity. Cyclohexene oxide is epoxy. Octane give some products attributable to epoxy carbonylation. oxide. The reaction conditions for these latter epoxides may perhaps be optimized for better yield and selectivity.

The carbonylation reaction, as indicated above, rea. It is used in a suitable solvent. As a general principle, solvents which may be classified as having medium or high polarity are suitable: for example aromatic solvents. ethers, ethers, polyethers, sulfones and alcohols. Ketones and esters may also be used depending on the reactivity of the chosen solvent and the specific conditions to be used. Preferred solvents are generally ethers, po. high molecular weight cyclic ethers and ethers, especially glycol polyethers. An especially preferred solvent is tetraglyme, tetraethylene glycol dimethyl ether, or 2,5,8,11,14-penta-oxapentadecane. Particularly useful solvents are tetrahydrofuran, diglyme and oils.

R

Ucon, mixed glycol polyethers of ethylene glycol and propylene glycol subunits.

For a solvent to be suitable it should solubilize the epoxide reagent and should not react adversely with any of the components of the reaction mixture or with the desired product. Thus for low molecular weight epoxides and glycols solvents such as tetraglyme, tetrahydrofuran and the like are usually employed. For epoxides and gli66 580

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Higher molecular weight hydrocarbon solvents such as petroleum ethers, toluene and xylene may be suitable. The latter solvents are less suitable for lower molecular weight epoxides and glycols such as ethylene oxide and 1.5-propanediol. These hydrocarbon solvents? These are not suitable as low molecular weight epoxides are insoluble in them and separate from solvents.

Rhodium, used in the present process, may be introduced in the form of metallic rhodium, rhodium oxides, rhodium salts and / or rhodium complexes. The only limit

The point is that the rhodium complex does not contain ligands that will insolubilize or poison the catalyst. Thus, the selection of the specific rhodium component may in part depend upon the solubility of the metallic rhodium or rhodium compound in the solvent chosen for the reaction medium. Useful form of rhodium in the practice of the present invention includes rhodium metal, rhodium oxides, R1H4, RhBr4, RhCl4, Rh (Acac) 4, Rh (C0)₂Acac / RhCl (C0)₂_7₂ and Rh1NO4), where AcaG represents acetyl acetonate. Similarly, the rhodium form useful in the practice of the present invention may be a rhodium carbonyl phosphine complex which has been pre-prepared (prior to introduction into the reaction mixture) using any suitable technique for pre-preparation of these complexes. The rhodium concentration in the "reaction solvent" should be in the concentration range from about 0.00001 molar to about 0.1 molar. Preferably the rhodium concentration will be between about 0.005 and about 0.05 molar.

The phosphine used in the present invention has the formula wherein R1, R2 and R3 are independently selected from the group consisting of aliphatic and aromatic radicals. Preferably R4, R₂ and R 4 are all alkyl groups containing from about 1 to about 12 carbon atoms. Particularly preferred alkyl groups are n-propyl, i-propyl, n-butyl, i-butyl and cyclohexyl. The aryl-

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Aryl / alkyl phosphine mixtures may be used in the present invention but their effectiveness depends on the reaction particle conditions used, including the solvent. In general, aryl- and aryl- alkylphosphine mixtures are not as effective as tri-alkylphosphines. The preferred phosphine is tri cyclohexylphosphine. Triisopropylphosphine and triisobutylphosphine have also been found to be extremely useful.

The amount of phosphine used is not very important but it has been found that a rhodium: phosphine molar ratio of about 1: 1 is generally preferred. More broadly, however,

I operating a range between about 10: 1 and about 1:10. The rhodium: phosphine molar ratio will typically be between about 2: 1 and about 1: 2.

The presence of acid in the reaction mixture has been found to be useful in obtaining optimal results. Usually strong and medium acids are preferred in the present process. Some acids, however, are less desirable due to their corrosiveness or insolubility, especially of the corresponding anion in the particularly used solvent. Halotenides in particular may promote sun decomposition. etheric agents and this would be undesirable in such solvents. However, acids HI and HCl are useful in this process.

Preferred acids are phosphoric acid and para-toluenesulfonic acid. It may operate on weaker acids such as acetic, depending on the particular reaction conditions, but may also be esterified.

Usually the amount of acid, if present, will be approximately equal to the molar amount of rhodium and / or phosphine. When using acid, the preferred molar ratio of rhodium: phosphine: acid is approximately 1: 1: 1. As a general rule it has been found that varying the molar ratio by factors from 2 to 5 only results in slightly detrimental effects. The acid: phosphine molar ratio typically should not exceed 5: 1. The presence of an acid is believed to be important to minimize the formation of by-products. Thus, the acid, when present in sufficient quantity, will tend to neutralize strong components.

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It is important that, in a basic environment, aldehydes tend to undergo condensation reactions thus forming undesirable by-products.

The hydrogen: carbon monoxide ratio used in the hydroformylation reaction was not found to be very important. In general a H2 SO2 ratio between about 10: 1 and about 1:10 is usable. Typically a ratio of about 5: 1 to about 1: 1 is used. In general it has been found that yields increase when the ratio H₂: CQ.

With respect to the pressure used during the hydroformylation reaction, the pressure is not very important and generally ranges from about 200 to about 10,000 psig. Preferably the pressure will be between about 1,000 and about 4,000 psig. Generally it has been found that both velocities and selectivities are improved by the hydrogen partial pressure range. However, increasing the partial pressure of carbon monoxide can be detrimental.

With respect to the conversion of ethylene oxide to 1,3-propanediol the rate of product formation increases by a factor of 2-3 as the hydrogen partial pressure increases from about 500 to about 2,000 psig. When the carbon monoxide partial pressure increases from about 500 to about 1,000 psig there seems to be a slight increase in the rate of product formation but when the partial pressure increases further from 1,000 to 2,000 psig the Propanediol-1,3 formation decays rapidly.

Regarding the effect of pressure on the efficiency of conversion to propanediol-1,3, the trends are similar to those cited for conversion rates. Thus, when hydrogen partial pressure is increased from 500 to 1,000 psig and then to 2,000 psig, selectivity for propanediol-1,3 increases dramatically while selectivity is increased. of for C products₂ and C? decreases.

The temperature used in the carbonylation reaction also

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It is not fundamental. As a general rule it has been found that increasing the temperature also increases the speed of the reaction. Increasing temperature however has an adverse effect on selectivity. Thus it is necessary to regulate the temperature to obtain adequate speeds and proper selectivities. In general, a temperature of from about 50 to about 200 ° C, preferably from about 100 to about 150 ° C, is employed.

In the preparation of propanediol-1.3 the rhodium, tricyclohexylphosphine and phosphoric acid system at 2500 psig in tetraglyme as solvent containing 0.69M water at 110BC temperature results in an efficiency of 85 to 90% but if we increase the temperature to 130qC, the efficiency drops to 70-75 $. It is also found that when the temperature rises, the induction period also decreases.

With respect to the F 2 / CO composition in general the reaction pressure and temperature vary somewhat with the conditions used for the reaction and its adjustment is within the ordinary experience of the operator.

Water is generally found to be useful in conjunction with many catalysts and solvent / acid combinations. In particular, while water is not required for the function of the catalysts used in this invention, in the absence of water substantial induction periods are sometimes observed between the injection of ethylene oxide and the start of synthesis gas uptake. the formation of the reaction product, for example, propanediol-1,3. It has been found that the presence of small amounts of water can sometimes substantially reduce the duration of induction periods and thus shorten the total reaction time. However, if the amount of water increases beyond a certain level, lower yields may result.

More broadly, water is used from about 0.00 to about 25% by weight, preferably from about 0.00 to about 10% by weight. The amount of water used to achieve optimal results, as indicated above,

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'12 will depend on the particular reaction system and the conditions adopted.

With respect to the production of 1,3-propanediol, using the catalyst system comprising radio, tricyclohexylphosph. at 1109C, 2500 psig pressure and a hydrogen: carbon monoxide ratio of 2: 1 in tetraglimate solvent, it was found that by reducing the water concentration from 3.47M to 0, the efficiency of conversion improved substantially from 70-75% to 85-88%. Although some efficiency improvement was expected due to the reduction of

In losses caused by hydrolysis of ethylene oxide, the reasons for such a large increase in efficiency are unknown and quite unexpected. Similarly, the reduction in the induction period, the time required before taking up the synthesis gas after ethylene oxide injection, also increased unexpectedly. Thus, at a water concentration of 3.47M, the induction period is typically in the range of 30 to 40 minutes and the total duration of operation of 4 to 5 hours. 0 Induction period increases only slightly when water concentration is reduced to about 0.69M. However, as further reductions in water concentration are made, induction periods dramatically increase to approximately 3 hours. Importantly, after the synthesis gas intake begins, regardless of the initially present water concentrations, the velocities of the synthesis gas intake are approximately equivalent.

The present invention makes it possible to produce 1,3-glycols, such as propanediol-1,3, above 85% based on the weight of epoxide as ethylene oxide and to obtain production speeds of the order of 0.92. mol / liter / hour in a single carbonylation reactor. These results are certainly unexpected and surprising since the use of rhodium catalysts for carbonylation of epoxides in 1,3-glycols had never been shown. The present results are also surprising given that most previously used cobalt catalysts only achieved substantially lower reaction rates and efficiencies.

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propanediol-1,3 precursors, while the present process yields a high single-step yield of 1,3-glycols without the need for large independent hydrogenation reactors. precursors of 1,3-glycols.

The present invention is illustrated below by examples without limitation.

General Experimental Process Used in the Examples

All examples were run on a 300 cc Hastelloy batch flushing unit equipped with remote controls for power, ventilation, stirring, heating, cooling and others. When reactor pressures were low, standard stainless steel tubing and Suagelok fittings were used. At pressures of 2500 psig, high pressure fittings, valves, and piping were used.

All catalysts and solvents were weighed under nitrogen and rapidly introduced into a cold autoclave which was then purged twice with nitrogen and twice with synthesis gas. Then the autoclave was pressurized with synthesis gas to the desired pressure and warmed to the reaction temperature with slow stirring over a period of 0.5 to 4.0 hours. 0 Ethylene oxide was then injected into the autoclave by a pressurized injection pump or a Ruska syringe pump, then starting a rapid agitation and raising the total reactor pressure to the desired end value using the synthesis gas to control the pressure. Reactor pressures were automatically maintained constant during operations by supplying the required synthesis gas from a well-known reservoir with high pressure synthesis gas. Reaction synthesis gas uptake was controlled by periodic measurement of the synthesis gas reservoir pressure. Operations usually ended when the synthesis gas intake dropped to near zero; by decreasing the stirring rate, terminating the introduction of synthesis gas and cooling the reactor as quickly as possible, typically while

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Over a period of 30 to 60 minutes.

Small amounts of ethylene oxide were injected into the reactor, hot and pressurized, using a Ruska syringe or a pressurized injection pump. When the latter method was used, ethylene oxide was introduced into the injection pump by condensing ethylene oxide vapor from a lecture bottle into the injection pump by cooling it to the temperature of carbon dioxide. After loading the injection pump with ethylene oxide, the pump was separated from the transfer device, weighed and then connected to the autoclave. Synthesis gas pressure was used to force the ethylene oxide out of the injection pump into the autoclave.

When the Ruska pump method was used to inject ethylene oxide, liquid ethylene oxide was transferred through stainless steel tubes into the Ruska syringe which then injected ethylene oxide into the autoclave unit.

As the pipes, fittings and valves, up to the autoclave, were retaining liquid ethylene oxide, it was necessary to introduce somewhat larger amounts of ethylene oxide into the injection pump or Ruska pump and then to calibrate the unit for actual amount of ethylene oxide that reached the autoclave. Calibration operations were conducted by loading the reactor with 100 grams of water and 1.8 grams of sulfuric acid and heating to 100 ° C. Ethylene oxide was then introduced into the injection pump or Ruska pump, injected into the reactor which was then heated for two hours to achieve hydrolysis of ethylene oxide in ethylene glycol. The resulting ethylene glycol: water solutions were analyzed for ethylene glycol using gas chromatography. In a typical operation, 12.0 grams of ethylene oxide introduced into the injection pump would give the reactor ethylene glycol equivalent to 10.0 grams of ethylene oxide. The ethylene oxide feed was then calculated in the opposite direction from ethylene66 580

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glycol and graphs of ethylene oxide were constructed. oxide versus charged ethylene oxide. These graphs were found to be fairly linear in the range of 5 to 15 grams of ethylene oxide and typically showed an efficiency of 75 to 85% of ethylene oxide in the transfer operation. The results of these calibration operations were then used to calculate the ethyl oxide in the introduced catalytic carbonylation operations.

For products used in the Examples, fZRhCl (C0) 2_72 » ^P^^Ç6^11^3 ^{and P}^^n_!4^9^3 ^^orani purchased from Strem Chemicals, stored and handled under a nitrogen atmosphere. Rh (C0)₂Acac was purchased either from Englehard or pre. It was quenched from RhCl ^3 (- ^ 0, acetylacetone and dimethylformamide and then recrystallized from hexane to give red-green crystalline needles.

Ethylene oxide (99.7% min) was purchased from Matheson and stored in cold water. The mixtures H₂/ C0 were acquired at Iu / echo. Tetraglyme and sulfolane were used in the tests as received from Aldrich as well as n-butanol received from Burdick and Dackson. Toluene and tetrahydrofuran, received from Aldrich, were distilled into metallic sodium under a nitrogen atmosphere.

In the accompanying examples, reaction products are sometimes divided into four categories. PDO Precursors consist of propanediol-1,3 (PDO-1,5), 3-hydroxypropionaldehyde (HPA) and 2-hydroxyethyl-1,3-dioxane (HED). PDO Precursor products include, in addition to PDO-1,3, HPA and HED because, presumably, they could be hydrolyzed and / or hydrogenated to PDO-1,3. EtOH Precursors include acetaldehyde and ethanol. PrOH Precursors include acrolein, propionaldehyde and propanol. Other consists of all identified products that do not fall into any of the previous categories. In the examples where yields are cited these were calculated from the number of moles of product observed divided by the number of moles of E0 (calculated by the E0 calibration process).

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-16da in the reactor. In some cases, due to certain experimental errors in the ethylene oxide injection process and associated calibration process, the sum of the products analyzed derived from ethylene oxide slightly exceeded the calculated amount of ethylene oxide introduced into the reactor. . In such examples production efficiencies are indicated (for the purpose of beads they were normalized to 100% E0).

EXAMPLE 1 grams of tetraglyme, 0.50 grams of RhíCO ^ Acac,

1.1 grams of tricyclohexylphosphine and 0.1 grams of hydroquinone were placed in a 300 οιϊϊ autoclave according to standard procedures. The mixture was heated to 100 ° C under 1000 psig Hg / CO (2: 1), the reactor pressure was then increased to 1400 psig and 8.9 grams of ethylene oxide was injected with a Ruska pump. . In less than 25 minutes, H 2 / CD gas uptake began to take place._f 2: 1, and thereafter the pressure was maintained at 1400 psig by addition of ^H2 / c °, 2: 1 as required. The reaction ended after

4.6 hours (gas adsorption had not completely ceased) and the product which was analyzed by gas chromatography was removed. The product did not contain free propanediol-1,3 but contained small amounts of HPA (0.0016 mole) and HED (0.0002 mole). The major products were unconverted ethylene oxide (0.0895 mole), acrolein (0.0174 mole), ethylene glycol (0.0112 mole) and 2-methylpentanol (0.0097 mole). Minor amounts of acetaldehyde, propanol and 2-methylpentanal were also detected, simultaneously with small amounts of numerous other by-products. This example shows that ethylene oxide is carbonylated to Cj products by the use of Rh / phosphine catalysts in the absence of acid promoters. Only small amounts of PDO Precursor molecules were produced but substantial amounts of C4 products (presumably derived from the reaction of E0 with C0 and H were observed).₂). Substantial amounts of C1-4 products (which may result from the binding of C1-4 aldehydes) were also produced.

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EXAMPLE 2 grams of tetraglyme, 0.53 grams of RhCl2 Acac, 0.54 grams of tricyclohexylphosphine, 1.0 grams of 57% aqueous HI, 5.0 grams of H2O and 0.1 grams of hydroquinone were autoclaved and heated to 120 ° C under 1500 psig H 2 / CO 2: 1. Ethylene oxide (8.9 grams) was injected with a Ruska pump and then feed H₂/ C0, 2: 1, required to maintain a pressure of 1500 psig. The operation ended after 116 minutes. The product contained 0.057 mole PDO-1.3, 0.014 mole HPA and 0.012 mole HED, with a total yield of PDO Precursors of 47.4%. The major by-products were ethanol (0.045 mol), acetaldeldo (0.019 mol), propanal (0.009 mol), propanol (0.004 mol), 2-methylpentanal (0.006 mol) and

2-methylpentanol (0.005 mol). Traces of ethylene glycol and other unidentified products were also observed. This example illustrates the use of a promoter acid (H1) to enhance the activity and selectivity of a rhodium / phosphine catalyst for carbonylation of ethylene oxide in propanediol-1,3 at relatively low pressures.

EXAMPLE 3 grams of tetraglyme, 0.54 grams of hydrated rhodium trichloride, 0.53 grams of tricyclohexylphosphine, 0.20 grams of concentrated aqueous HCl, 5.11 grams of H₂0 and 0.11 grams of hydroquinone were placed in an autoclave. The mixture was heated to 120 ° C under 1000 psig H₂2: 1, 9.4 grams of ethylene oxide was injected with an injection pump using H₂/ C, 2: 1, and the final pressure was raised to 2500 psig. The gas intake started after approximately 50 minutes and the operation was completed 3 hours later, when the gas intake had practically stopped. The product was found to contain 0.1506 mole PDO-1.3 and 0.006 mole HPA in a combined yield of 73.4%. The major by-products included ethanol (0.053 mole), propa. nol (0.017 mole), ethylene glycol (0.013 mole) and ethylene oxide (0.003 mole). Due to the apparent yield

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In CO-derived molecules of 114.5%, the ethylene oxide efficiencies were normalized and PDO precursors with an efficiency of 64.9% had been formed at a rate of 0.626 moles / liter / hour. This example shows that 1,3-propanediol can be produced with reasonably good efficiency from a catalyst precursor that does not contain acetylacetonate ligands. It also illustrates the use of hydrochloric acid as a promoter.

EXAMPLE 4

80 grams of tetraglyme, 0.51 grams of RhíCO ^ Acac,

0.41 grams of triisobutylphosphine, 0.14 grams of phosphoric acid, 5.11 grams of H2 O and 0.1 grams of hydroquinone were autoclaved. The mixture was heated to 120 ° C under 1000 psig 1: 1 Ft / CO, then 10.0 grams of ethylene oxide was then injected with an injection pump and the pressure was raised to 2500 psig. Synthesis gas uptake started after about 40 minutes and the operation ended 3.6 hours later, when the gas uptake had practically ceased. Product analysis showed 0.166 mole PDO-1.3. The most important by-products included ethanol (0.0184 mole), acetaldehyde (0.0053 mole), ethylene glycol. col (0.012 mole), propanal (0.006 mole) and propanol (0.011 mole)¹ le). The yield of 1.3-propanediol was 74.3% at a speed of 0.567 mole / liter / hour. This example shows that propanediol-1,3 can be produced with good efficiency by using a trialkylphosphine other than tricyclohexylphosphine.

EXAMPLE 5 grams of tetraglyme, 0.52 grams of RhíCO ^ Acac, 0.54 grams of dicyclohexylphenylphosphine, 0.14 grams of acid. of the phosphorus, 5.1 grams of H2 O and 0.1 grams of hydroquinone were autoclaved and heated at 110 ° C under 1000 psig of H2 O / 2: 1. Ethylene oxide (10.1 grams) was injected with an injection pump and the pressure increased to 2500 psig. The gas intake started after about 1 hour and the

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The operation ended 6.5 hours later. Product analysis mos. showed the presence of 0.151 mole propanediol-1.3, 0.040 mole acetaldehyde, 0.027 mole ethanol and smaller amounts of acrolein, propanal, propanol and ethylene glycol. The 1.3-propanediol yield was calculated at 50% at a production rate of 0.22 mole / liter / hour. This example shows that propanediol-1,3 can be produced in reasonable yields by using a phosphine-promoted radio catalyst containing an aryl substituent.

EXAMPLE 6 grams of tetraglyme, 0.51 grams of RhíCO ^ Acac, 0.53 grams of tricyclohexylphosphine, 0.13 grams of phosphoric acid, 5.0 grams of Li ^O and 0.1 grams of hydroquinone were introduced. in an autoclave and heated to 11 ° C under 1000 psig H 2 / CO 2: 1. An injection pump injected ethylene oxide (10.2 grams) and increased the pressure to 2500 psig. The gas intake started after 50 minutes and the operation ended 4.0 hours later. 0 The product contained 0.1905 mole propane diol-1.3, 0.0235 mole ethanol, 0.0154 mole propanol, 0.0125 mole ethylene glycol and 0.0089 mole oxide. of ethylene. Because the apparent yield in E0-derived molecules was 110%, the ethylene oxide-based efficiencies were normalized and showed that propanediol-1,3 had formed with an efficiency of 77.5% at a rate of 0.595 mole / liter / hour. This example shows that propanediol-1,3 can be prepared with relatively good efficiency and speed by the use of a rhodium / phosphine catalyst promoted by water and phosphoric acid.

EXAMPLE 7 grams of tetraglyme, 0.52 grams of RhíCO ^ Acac, 0.53 grams of tricyclohexylphosphine, 0.13 grams of phosphoric acid, 1.05 grams of H2 O and 0.10 grams of hydroquinone were introduced. in an autoclave and heated to 110 ° C under 1000 psig h 2 / C 2: 1. With an injection pump ethylene oxide (10.0 grams) was injected and the pressure was increased to

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Docket No. C-7036

<img file="PT85558B_D0020.tif" />

Gas intake began after about 90 minutes and operation was finished 5.5 hours later. The product contained 0.1931 mole propanediol-1.3, 0.0172 mole ethanol, 0.0141 mole propanol and 0.0029 mol of ethylene oxide. Together, 1.3-propanediol was produced in a yield of 85% at a rate of 0.438 mole / liter / hour. This example we have. It is shown that efficiencies in propanediol-1,3 are somewhat improved when the amount of water decreases from the levels of the previous examples.

EXAMPLE 8 grams of tetraglyme, 0.52 grams of Rh (CO)₂Acac, 0.54 grams of tricyclohexylphosphine, 0.14 grams of phosphoric acid and 0.10 grams of hydroquinone were autoclaved. No water was added to the cargo. The mixture was heated to 110 ° C under 1000 psig H₂/ CO 2: 1. Ethylene oxide (10.0 grams) was injected with an injection pump and the pressure increased to 2500 psig. The gas intake started after about 160 minutes and the operation ended 6.5 hours after that. Product analysis showed the presence of 0.1983 mole propanediol-1.3, 0.0166 mole ethanol, 0.0046 mole acetaldehyde and 0.0092 mole propanol. The yield of 1.3-propanediol was 87% at a rate of 0.377 mole / liter / hour. This example shows that propanediol-1,3 can be produced in good yield in the absence of the water promoter, although induction periods are slightly longer in the absence of water.

EXAMPLE 9 grams of tetraglyme, 0.51 grams of RhfCO4 Acac, 0.54 grams of tricyclohexylphosphine, 0.13 grams of phosphoric acid and 1.05 grams of H₂0, were introduced into the autoclave. No hydroquinone was added. The mixture was heated to lioac under 1000 psig H₂2: 1, 10.1 grams of ethylene oxide was injected with an injection pump and the pressure increased to 2500 psig. The gas intake started after about 90 minutes and the operation ended 6.5 hours later.

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Docket No. C-7036

<img file="PT85558B_D0021.tif" />

Product analysis showed the presence of 0.2172 mole of propanediol-1.3, 0.0196 mole of ethanol, 0.0133 mole of propane, nol and traces of acetaldehyde and ethylene oxide. Because the apparent yield on ethylene oxide-derived molecules was 113%, the efficiencies in ethylene oxide were normalized and it was proved that propanediol-1,3 had been produced in 85% yield at a rate of 0.41 mole / liter / hour. This example shows that the absence of the hydroquinone promoter (which was included in many of the examples herein) had no substantial effect on the yield or production rate of 1,3-propanediol.

EXAMPLE 10 grams of Ucon 50-HB-1QQ polyglycol / ether, 0.52 grams of Rh (CO)₂Acac, 0.53 grams of tricyclohexylphosphine,

0.13 grams of phosphoric acid, 5.1 grams of H2 O and 0.1 grams of hydroquinone were autoclaved and heated to 1109 ° C under 1000 psig H₂/ CO 2: 1. An injection pump was injected with ethylene oxide (10.0 grams) and the pressure increased to 2500 psig. The gas intake started after about 20 minutes and the operation ended 3.0 hours later.

Product analysis showed the presence of 0.1775 mole propanediol-1.3, 0.0243 mole propanol, 0.0269 mole ethanol, 0.0125 mole acetaldehyde, 0.0102 mole acrolein and traces of ethylene oxide and ethylene glycol. Due to the apparent yield on molecules derived from ethylene oxide being 112%, the efficiency of ethylene oxide was normalized and it was proved that propanediol-1,3 was produced at 70.2% efficiency. velocity of 0.717 mole / liter / hour. This example shows that propanediol-1,3 can be produced with good efficiencies in a complex polyglycol / ether solvent other than tetraglyme.

EXAMPLE 11 grams tetrahydrofuran, 0.52 grams Rh (CO)₂Acac, 0.54 grams of tricyclohexylphosphine, 0.13 grams of

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Docket No. C-7036

<img file="PT85558B_D0022.tif" />

Phosphoric acid, 5.1 grams of H2 O and 0.10 grams of hydroquinone were autoclaved and heated to 110Â °.

C under 1000 psig F 2 / CO 2: 1. An injection pump injected ethylene oxide (1.0 grams) and increased the pressure to 2500 psig. The gas intake started about 40 minutes later and the operation ended after 3.5 hours. Product analysis showed the presence of 0.2058 mole propanediol-1.3, 0.0166 mole ethanol, 0.0114 mole propanol and 0.0026 mole acrolein. Because the apparent yield in ethylene oxide derived molecules is 106%, the efficiencies of ethylene oxide have been normalized showing that propanediol-1.3 was produced with an efficiency of 85.8 $ at a speed of 0.739 mole. / liter / hour. This example shows that 1,3-propanediol can be produced with high efficiency in a monoether solvent and that it is extremely unlikely that 1,3-propanediol can derive from solvent decomposition.

EXAMPLE 12 grams of tetraglyme, 0.51 grams of RhCCO4 Acac, 0.54 grams of tricyclohexylphosphine, 0.14 grams of phosphoric acid, 5.11 grams of H2 O and 0.11 grams of hydroquinone were introduced. in the autoclave and heated to 110 ° C under 1000 psig F 2 / CO 2: 1. Propylene oxide (15.8 grams) was introduced into an injection pump which was then injected into the autoclave. No attempt has been made to calibrate the pej? propylene oxide during the injection operation. The gas intake started after 2.5 hours and the operation ended after 7.5 hours before the gas intake ceased. The liquid product (101.7 grams) was collected and analyzed by GC and GC-mass spectrum. The product was found to contain approximately 7.8 wt% unconverted propylene oxide, about 5.5 wt% butanediol-1.3 and about 0.5 wt% propylene glycol-1,2. No other significant products were detected. Although not optimized, this example shows that propanediol-1,3 can be produced via propylene oxide carbonylation relatively selectively.