JPH0351462B2 - - Google Patents

Description

Claim 1: Calcium oxide, calcium hydroxide, or mixtures thereof are at least partially solubilized by mixing with the active agent ethylene glycol, thereby producing a calcium-containing composition with titratable alkalinity. A method for producing an alkoxylation catalyst, the method comprising: 2 Calcium oxide, calcium hydroxide, or mixtures thereof are at least partially solubilized by mixing with the active agent ethylene glycol, thereby producing a calcium-containing composition with titratable alkalinity; A method for producing an alkoxylation catalyst, characterized in that the calcium-containing composition and alcohol are reacted under alcohol exchange reaction conditions, thereby producing the corresponding alcohol derivative of the calcium-containing composition. 3. The method according to claim 2, wherein the alcohol is n-dodecanol. 4. The method according to claim 2, wherein the alcohol is a mixture of C ₁₂ alcohol and C ₁₄ alcohol. 5 Calcium oxide, calcium hydroxide or mixtures thereof are at least partially solubilized by mixing with the active agent ethylene glycol, thereby producing a calcium-containing composition with titratable alkalinity, and then A method for producing an alkoxylation catalyst, characterized in that some or all of the activator not bound to calcium is removed. 6 Calcium oxide, calcium hydroxide, or mixtures thereof are at least partially solubilized by mixing with the active agent ethylene glycol, thereby producing a calcium-containing composition with titratable alkalinity; removing some or all of the active agent not bound to the
A method for producing an alkoxylation catalyst, characterized in that the product composition and alcohol are then reacted under alcohol exchange reaction conditions, thereby producing the corresponding alcohol derivative of the calcium-containing composition. 7 Calcium oxide, calcium hydroxide, or mixtures thereof are at least partially solubilized by mixing with the active agent ethylene glycol, thereby producing a calcium-containing composition with titratable alkalinity, and then A method for producing an alkoxylation catalyst characterized in that a sufficient amount of a polyhydric oxyacid is added to neutralize a portion of the alkalinity of the product composition. 8. The method according to claim 7, wherein the oxyacid is sulfuric acid. 9. A method according to claim 7, which neutralizes 25 to 75% of the titratable alkalinity. 10. The method according to claim 9, which neutralizes 40 to 60% of the titratable alkalinity. 11 Calcium oxide, calcium hydroxide, or mixtures thereof are at least partially solubilized by mixing with the active agent ethylene glycol, thereby producing a calcium-containing composition with titratable alkalinity; Addition of a sufficient amount of a hydroxyacid to neutralize some of the alkalinity of the product, and then reacting the product composition with an alcohol under alcohol exchange reaction conditions, thereby modifying the composition of the calcium-containing composition. 1. A method for producing an alkoxylation catalyst, which comprises producing an alcohol derivative. 12 Claim 1 in which the oxyacid is sulfuric acid
The method described in Section 1. 13. The method of claim 11, wherein 25 to 75% of the titratable alkalinity is neutralized. 14. The method of claim 13, wherein 40 to 60% of the titratable alkalinity is neutralized. FIELD OF THE INVENTION The present invention relates to a process for preparing calcium-containing catalysts for alkoxylation using calcium oxide, calcium hydroxide or mixtures thereof. Background to Alkoxylation Products Various products such as surfactants, functional fluids, glycol ethers, polyols, etc. commonly combine epoxides with at least one active hydrogen in the presence of alkaline or acidic catalysts. It is produced industrially by a condensation reaction with an organic compound containing The type and nature of the alkoxylation product is related, inter alia, to the active hydrogen compound, epoxide, and molar ratio of epoxide to organic compound used, as well as the catalyst. As a result of alkoxylation, a mixture of condensation product species having a range of molecular weights is obtained. In many applications of alkoxylated products,
Some alkoxylated species exhibit much greater activity than others. It is therefore desirable that the alkoxylation process be selective for the production of these alkoxylated species. Furthermore, for many of these applications, mixtures of alkoxylated products within a narrow molecular distribution range of the reacted epoxide appear to be superior to alkoxylated products dominated by a single alkoxylated product species. . For example, in a surfactant composition, the range of substances on which a surfactant needs to act typically varies. A range of alkoxylated species, even if narrow, enhances the surfactant's performance against the variety of materials it may encounter. Furthermore, mixtures of closely related alkoxylated species have superior cloud points, freezing points,
Mixtures can be provided with other properties such as pour point and viscosity. However, an equilibrium exists and if the distribution of the alkoxylated species becomes too broad, the less desirable alkoxylated species will not only dilute the mixture, but also make it more hydrophobic or lipophilic than in the range being sought. components may be detrimental to the property being sought. Furthermore, the wide range of alkoxylated species can limit the flexibility in the final product formulation using the alkoxylated reaction product.
For example, in the production of oil-in-water emulsion products, it is often desirable to prepare concentrated compositions that minimize the weight percentage of water. This concentrate can be diluted with water at the time of use, thereby saving water for transport and storage. The ability to form desirable concentrates is generally related in part to having a narrow distribution of alkoxylated species. Because the heavy fraction of the alkoxylated species is present, a larger proportion of water is usually required, otherwise gelation (manifesting instability of the product) may occur. It has long been recognized that a certain proportion of moles of epoxide to moles of organic compound in the alkoxylation product may be important. For example, British Patent Specification No. 1399966 for use in laundry detergents
Hydrophilic-lipophilic balance (HLB) of about 10 to about 13.5
discloses the use of ethoxylates having
The number of moles of ethylene oxide reacted per mole of fatty alcohol is stated to be critical in order to provide this HLB. The laundry compositions explored in British Patent Specification No. 1462133 are very narrow, ie from about 10 to about 12.5
Sufficient alkylene oxide cosurfactant was used to give HLB. British Patent Specification No.
No. 1462134, ethoxylates having an HLB of about 9.5 to 11.5, preferably 10.0 to 11.1
Detergent compositions are disclosed that use ethoxylates having an HLB of . Thus, as our understanding of the properties to be imparted by alkoxylated products increases, there is an increasing need to adapt the production of alkoxylated products to enhance the properties sought. It is. Efforts have therefore been made to provide alkoxylation products in which the distribution of reacted epoxide per mole of organic compound is limited to a range that enhances the properties sought. Alkoxylation Process The alkoxylation process is characterized by a condensation reaction in the presence of at least one epoxide and at least one organic compound having at least one active hydrogen. Perhaps the most common catalyst is potassium hydroxide. However, products made using potassium hydroxide generally exhibit a wide distribution of alkoxylate species. See, for example, M. J. Shick, "Nonionic Surf Actant", Volume 1, Marcel Detzker & Co., New York, NY (1967), pp. 28-41. That is, little selectivity is shown for individual alkoxylate species, especially at high alkoxylation ratios. For example, Figure 6 of US Pat. No. 4,223,164 shows the distribution of alkoxylate species prepared by ethoxylating a fatty alcohol mixture with 60% by weight ethylene oxide using a potassium catalyst. The distribution obtained in the alkoxylation process varies depending on the type of organic compound to be alkoxylated even when the same type of catalyst is used. For example, for nonylphenol, a Poisson type distribution can be obtained using potassium hydroxide as a catalyst. However, for aliphatic alcohols such as decanol, dodecanol, etc., the distribution is certainly wide. These distributions are referred to herein as "conventional broad distributions." Acidic catalysts can also be used; they tend to produce narrower and therefore more desirable molecular weight distributions. However, they also cause the production of undesired by-products and are therefore not widely used industrially. Particular emphasis has been placed on controlling the molecular weight distribution of alkoxylation products. One of the studies was to strip unwanted alkoxylate species from the product mixture. For example, US Pat. No. 3,682,849 discloses a method for gas phase removal of unreacted alcohol and low boiling ethoxylated components. The composition comprises up to about 1% by weight of each non-ethoxylated alcohol and monoethoxylate, up to 2% by weight diethoxylate and 3% by weight.
It is said to contain the following triethoxylates. This process results in a loss of raw material as lower ethoxylates are removed from the composition. Also, the stripped product still has a broad distribution of ethoxylate species, ie, there is still a significant amount of high molecular weight product present in the composition. approximately 20 to 30% of the starting alcohol to avoid viscosity problems normally present with straight chain alcohols.
should be branched out according to the patent specification. Obtaining a narrow distribution of alkoxylated species at low epoxide reactant to organic compound molar ratios can be easily achieved. US Patent No.
No. 4,098,818 discloses a process in which the molar ratio of catalyst (eg, alkali metal or alkali metal hydride) to fatty alcohol is about 1:1. The ethoxylate distribution is described in Parts C and D of Example 1 and summarized below.

It is clear that a high catalyst content combined with a low epoxide to alcohol ratio allows the production of a narrow, lower ethoxylate fraction. However, as the epoxide to alcohol ratio increases, one can expect the characteristic "normal wide distribution" of alkali metal catalysts. Moreover, even though the disclosed method is reported to give a narrower distribution of ethoxylate species, the distribution is skewed such that a significant amount of higher ethoxylates are present. For example, more than 15% of the ethoxylate compounds in Part C had at least 3 more oxyethylene groups than the average based on the reactants, and the amount in Part D was more than 16%. European patent application published on December 12, 1983
A0095562 (see JP 58-210859) describes the ability to obtain high selectivity towards lower ethoxylate species, as well as the ability to obtain higher ethoxylated products when low ratios of ethylene oxide reactant to alcohol are employed. This example illustrates the tendency for the selectivity to loosen rapidly when For example, Example 1 reporting the use of diethylaluminium fluoride catalyst (described as a 1 mole EO adduct) used 300 g of an alcohol having 12 to 14 carbons and 64 g of ethylene oxide;
Example 5 (described as a 1.5 mole EO adduct) using the same catalyst employs an alcohol to ethylene oxide weight ratio of 300:118. Based on the data presented graphically, the distribution appears to be as follows: Example 1 Example 5 E ₀ 27 10 E ₁ 50 36 E ₂ 17 33 E ₃ 4 16 E ₄ − 6 E ₅ − 2 E ₆ - 1 1.5 described from 1 mole EO adduct described
With a slight increase in ethoxylation to molar EO adducts, the distribution of ethoxylate species has broadened considerably with the formation of more higher ethoxylates as can be expected from the "conventional wide distribution". . It is likely that the catalyst is consumed during the reaction process and therefore cannot be utilized to give a narrower distribution of the alkoxylation product mixture at high addition levels. Several catalysts were identified that were reported to give higher ethoxylates a narrower molecular weight distribution than would be expected from a "conventional broad distribution." In particular, this study highlighted ethoxylation catalysis by Group A alkaline earth metal derivatives.
Their importance in these catalysts, which until now have been almost exclusively limited to the production of nonionic surfactants, is due to their narrower molecular weight range than their counterparts produced using conventional alkali metal-derived catalysts. based on the proven ability of these catalysts to produce hydrophobe ethoxylates with improved distribution, lower unreacted alcohol content, and lower pour points. Recently, Yang and his co-workers have been granted a series of US patents which primarily focus on the production of the corresponding products produced by state-of-the-art catalysis with alkali metal hydroxides. Unmodified or phenolic modified barium and strontium as ethoxylation catalysts to produce nonionic surfactants exhibiting lower pour points, narrower molecular weight distributions, lower unreacted alcohol content and better detergency. discloses the use of purified oxides and hydroxides. U.S. Patent Nos. 4210764; 4223164; 4239917;
Reference should be made to the specifications of No. 4254287; No. 4302613 and No. 4306093. Significantly, these patents show that magnesium and calcium oxides and/or hydroxides can function in the role of cocatalysts for barium and strontium compounds, but have no catalytic activity for ethoxylation. It includes a description of the effect of not showing. Although the molecular weight distributions of the ethoxylates disclosed in these patent specifications are narrower than conventional distributions, they do not seem to fully satisfy the desired narrowness. For example, Figure 6 of U.S. Pat. No. 4,223,146 shows the product distribution of ethoxylates of alcohols having 12 to 14 carbon atoms and 60% ethylene oxide using various catalysts. A barium hydroxide catalyst is described as providing a product mixture containing about 16% of 6 mole ethoxylate as the predominant component. However, the distribution is still comparable in that ethoxylate species with 3 or more oxyethylene groups than the most predominant component account for more than 19% by weight of the mixture, skewing the distribution towards higher ethoxylates. wide. The strontium hydroxide catalyst experiment described in the figure above also appears to have a more symmetrical distribution, but with approximately 14.5% by weight of the 7 mole ethoxylate being the predominant component, and the composition 21% by weight of the material had 3 or more oxyethylene groups than the most predominant component. US Pat. No. 4,239,917 also discloses ethoxylate distributions using barium hydroxide catalysts and fatty alcohols. Figure 7 of the patent specification illustrates the distribution at the 40% ethoxylation level for the most predominant component, 4 mole ethoxylate. About 19% by weight or more of the mixture has 3 or more oxyethylene groups than the most predominant component. Figure 4 shows the distribution of ethoxylation at the 65% ethoxylation level. The 9 and 10 mole ethoxylates are the most predominant, each representing about 13% by weight of the composition. Although the distribution is relatively symmetrical, about 17% by weight of the composition has at least 3 more oxyethylene groups than the average peak (9.5 oxyethylene groups). Interestingly, for each of these figures, a comparative example using a sodium hydroxide catalyst is shown.
It demonstrates peak attainment that can be achieved with conventional base catalysis at low ethoxylation levels, but not at higher ethoxylation levels. Introduction of Calcium-Containing Catalysts McCain and co-workers have published a series of European patent applications describing the catalytic use of basic salts of alkaline earth metals, particularly calcium, that are soluble in the reaction medium. These applications further disclose catalyst preparation procedures that involve alcohol exchange for the alkoxy moiety of the metal alkoxide catalyst species. European Patent Application No.
Reference should be made to specifications 0026544, 0026547 and 0026546. Reference should also be made to U.S. Patent Application Serial No. 454,560 (Barium-Containing Catalysts), filed December 30, 1982. These researchers also disclose the use of strong acids to partially neutralize certain alkaline earth metal derivatives, thereby promoting catalysis. U.S. Patent Application Serial No. 370204, filed April 21, 1982, and December 1982, both of which are incorporated herein by reference.
Reference should be made to U.S. Patent Application Ser. These researchers also tended to confirm the findings of Young et al. on calcium oxide, in which Matsukane et al. taught that calcium oxide does not form lower alkoxides when treated with ethanol. are doing. In particular, calcium metal and calcium hydride are typical starting materials used by Matzukain et al. to produce calcium-containing catalysts. However, these starting materials are expensive. Therefore, calcium oxide (quicklime) is used to produce calcium-containing catalysts for alkoxylation.
There is a desire to use commonly found sources of calcium such as calcium hydroxide (slaked lime) and calcium hydroxide (slaked lime). Moreover, quicklime and slaked lime are by far the cheapest, most abundant, least harmful, and most environmentally acceptable of all alkaline earth metal derivatives. The calcium-containing catalyst disclosed by Matzukane et al. provides increased selectivity for higher alkoxylate species compared to mixtures produced using conventional potassium hydroxide catalysts. Indeed, there is reason to believe that these calcium-containing catalysts provide a narrower alkoxylate distribution than that provided by strontium- or barium-containing catalysts. However, a narrower distribution of alkoxylation products, especially alkoxylation products in which at least one component constitutes at least 20% by weight of the composition and in which there are more than 3 alkoxyl groups than the average peak of the alkoxylation components. There is still a need for a distribution in which the product constitutes very little of the product mixture. SUMMARY OF THE INVENTION The present invention provides a method for making an alkoxylation catalyst using calcium oxide and/or calcium hydroxide as a source of catalytically active calcium. or at least partially solubilizing calcium hydroxide. As used herein, the term "solubilized" means that the calcium is provided in the active form, rather than in the form of calcium oxide and/or calcium hydroxide, and therefore solubilization is assumed to be present. It is something. However, the term is not intended to be limited to the formation of actual dissolved calcium species, which may or may not be present. Solubilization involves mixing any calcium oxide and/or calcium hydroxide with the activator ethylene glycol, thereby creating a substantially This is done by forming a solid catalyst. Solubilization of calcium oxide or calcium hydroxide results in the production of an alkaline slurry. The alkalinity of the alkaline slurry can be detected and measured by titration, and is referred to herein as "titratable alkalinity." The catalyst composition, if it has active hydrogen, can be contacted directly with an alkylene oxide to form an alkoxylate of the activator itself to produce an alkoxylate. If the activator does not contain active hydrogen, excess activator should preferably be removed prior to alkoxylation. According to another embodiment of this aspect of the invention, after the reaction of the calcium oxide or calcium hydroxide with the activator, having an active hydrogen, such as an alcohol, under conditions in which an exchange reaction takes place;
Higher boiling point (and usually longer carbon chain length)
to produce the corresponding catalytically active high-boiling derivative of calcium. This latter catalytic species can then be contacted directly with an alkylene oxide to produce the high boiling material alkoxylate. In a particularly preferred embodiment of the invention, the calcium-containing composition (containing either the activator or the exchanged high-boiling substance) is contacted with a strong acid, preferably an oxyacid, and thereby partially neutralized. to produce a substantially solid composition. The compositions are also catalytically active in the alkoxylation of organic compounds having at least one active hydrogen and provide a narrower molecular weight distribution of alkoxylates than is obtainable with untreated catalysts.
This acid treatment can be performed either before or after removal of the activator. Discussion of mixtures of alkoxylated products ^The mixture _of alkoxylated products has the _formula ^: is an organic residue, m is an integer from at least 1 to the number of active hydrogens contained in the organic compound, and R ¹ and R ² may be the same or different; to 28 alkyl (including hydroxy-substituted alkyl and halo-substituted alkyl), where n is an integer of at least 1, such as from 1 to about 50.
It includes alkoxylated species which can be represented by. Organic compounds with active hydrogen include alcohols (monohydric, dihydric and polyhydric alcohols), phenols, carboxylic acids (mono, di and polyacids), and amines (primary and secondary). Often the organic compounds contain from 1 carbon to about 100 or 150 carbons (in the case of polyol polymers) and may contain aliphatic and/or aromatic structures. Most often the organic compound can be selected from monohydric, dihydric and trihydric alcohols having from 1 to about 30 carbon atoms. Particularly preferred alcohols include methanol, ethanol, propanol, pentanol, hexanol, heptanol, octanol, nonanol,
Decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol, isopropyl alcohol, 2-ethylhexanol, secondary butanol, isobutanol, 2-pentanol, 3-pentanol and Primary and secondary monohydric alcohols, which may be straight or branched, such as isodecanol. Particularly preferred alcohols are linear and branched primary alcohols (including mixtures) such as those produced by the "oxo" reaction of _C3 to _C20 olefins. The alcohol may be a cycloaliphatic alcohol such as cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, and aromatic substituted aliphatic alcohols such as benzyl alcohol, phenylethyl alcohol and phenylpropyl alcohol. . Other aliphatic structures are 2
-Includes methoxyethanol and the like. Phenols include alkylphenyls of up to 30 carbons such as p-methylphenol, p-ethylphenol, p-butylphenol, p-heptylphenol, p-nonylphenol, dinonylphenol and p-decylphenol. Aromatic groups can have other substituents such as halogen atoms. Alcohols (polyols) having two or more hydroxyl groups, such as about 2 to 6 hydroxyl groups and 2 to 30 carbons, include ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, Includes glycols such as neopentylene glycol, decylene glycol, diethylene glycol, triethylene glycol and dipropylene glycol. Other polyols include glycerin, 1,3-propanediol, pentaerythritol, galactitol, sorbitol, mannitol, erythritol, trimethylolethane and trimethylolpropane. The epoxides providing the oxyalkylene units in the ethoxylation product are ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2- and 2,3-pentylene oxide, cyclohexylene oxide, 1,2-hexylene oxide, 1,2
- alkylene oxides such as octylene oxide and 1,2-decylene oxide; epoxidized fatty alcohols such as epoxidized soybean fatty alcohol and epoxidized soybean fatty alcohol; such as styrene oxide and 2-methylstyrene oxide; aromatic epoxides; and hydroxy- and halogen-substituted epoxides such as glycidol, epichlorohydrin and epibromohydrin. Preferred epoxides are ethylene oxide and propylene oxide. The choice of organic residue and oxyalkylene moiety is based on the particular use of the resulting alkoxylated product. Advantageously, narrow distributions can be obtained using a wide variety of compounds with active hydrogen, especially monohydric alcohols, which provide the desired surfactants. Particularly attractive alkoxylated products are surfactants where, because of the narrow distribution of the alkoxylated products, a certain balance of hydrophilicity and lipophilicity is sought. Therefore, the organic compounds often include monohydric alcohols of about 8 to 20 carbons, and the epoxides include ethylene oxide. The method described here uses 1 mole of active hydrogen sites.
Although it is possible to selectively provide a narrow distribution of the most predominant alkoxylates with as low as molar oxyalkylenes, a particular advantage is that higher levels of alkoxylation, e.g. of oxyalkylene units, it has the ability to give a narrow distribution. For some surfactant applications, the most predominant alkoxylated species are 6, 7, 8,
It has 9, 10, 11 or 12 oxyalkylene units. For many surfactant applications, a relatively small number of species have been found to provide the desired activity, ie, a range of plus or minus 2 oxyalkylene units. The compositions of the invention are therefore particularly attractive in that the range of alkoxylation is narrow, but not so narrow that the range of activity is lost. Furthermore, the relatively symmetrical distribution of alkoxylate species that can be provided by the present invention enhances the balance of the distribution while maintaining desirable physical properties such as cloud point, freezing point, viscosity, pour point, etc. Provide the mixture shown. plus or minus 2 for many alkoxylation mixtures of the present invention.
Species within the range constitute at least 75%, such as about 80 to 95%, and in some cases 85 to 95%, by weight of the composition. Importantly, most often the most predominant species is
from about 30% by weight, such as from about 22 to 28% by weight, to enhance the balance of the composition. Another class of alkoxylated product mixtures are polyethylene glycols. For example, triethylene glycol and tetraethylene glycol have found use in gas dehydration, solvent extraction, and other chemicals and compositions. These glycols can be produced by ethoxylation of ethylene glycol and diethylene glycol. The advantageous process of the invention allows ethoxylation products containing at least about 80, eg about 80 to 95% by weight of triethylene glycol and tetraethylene glycol. Discussion of Alkoxylation Processes The mixtures of alkoxylation products of the present invention can provide a limited narrow distribution of alkoxylation products through the use of a calcium-containing catalyst modified with sufficient strong inorganic oxyacid. . The alkoxylation conditions can be varied in other ways while still obtaining a narrow distribution of alkoxylate products. The catalyst reforming acid is preferably a polyhydric acid and has at least one, and most often at least about two, oxygen atoms conventionally represented as double bonds to the nuclear atom. be. Such acids include sulfuric acid and phosphoric acid. However, generally the narrowest distribution is obtained using sulfuric acid. The amount of acid used to prepare the catalyst and the method of introduction are determined to achieve the desired narrow distribution in which at least one alkoxylated species is present in an amount of at least about 20% by weight of the composition. It may be a determining factor. Without wishing to be limited by theory, it is believed that the active catalyst for producing a narrow distribution of alkoxylation products consists of a calcium atom associated with an acid anion in a manner in which the calcium atom is activated. . For example, since calcium sulfate is inactive as an alkoxylation catalyst, the association between the calcium atom and the acid anion must be different from the association that forms a neutralized salt. Therefore, conditions that facilitate the formation of such salts should be avoided. Generally, during reforming, a calcium-containing catalyst has the formula: Ca(XR ³ H) _p (where p is 1 or 2,
XR ³ H is an organic-containing residue of an organic compound having active hydrogen, X being oxygen, nitrogen, sulfur or phosphorus). Therefore R ³
may have double bonded oxygen (the organic compound was a carboxylic acid) or may have oxygen, sulfur, nitrogen and phosphorus (for example, the organic compound may be a glycol,
There are also polyamines, glycol ethers, etc.). The amount of acid added is about 0.2 to 0.9 times, such as about 0.45 to 0.75 times, the amount required to neutralize the catalyst composition. Often the acid site (sulfuric acid has 2
The molar ratio of calcium atoms (phosphoric acid has 3 acid sites and phosphoric acid has 3 acid sites) is about 0.5:1 to 1.8:1. The acid is believed to enable the formation of the desired catalytically active calcium species. However, it has been found that, depending on the other conditions during the neutralization, different amounts of neutralization provide the optimum catalyst in terms of selectivity and reaction rate during the alkoxylation. As shown in Example 7, the highest selectivity for triethylene glycol and tetraethylene glycol was obtained in the experiment employing a neutralization level of 84.8% (Experiment 7). In Example 8, diethylene glycol rather than ethylene glycol was used as the medium during neutralization, and the dependence of selectivity on the degree of neutralization was less clear and the neutralization level
Experiment 1 gave the best selection with 74.7%. Example 8
It appears that the reaction rate increases with increasing degree of neutralization in the case of diethylene glycol medium in Example 7 (compare Experiments 1 and 17), but decreases with increasing degree of neutralization in the case of ethylene glycol medium in Example 7 ( It should also be noted that it appears (compare Experiments 5, 7, and 9). Therefore, one aspect of the present invention is to provide a level of neutralization sufficient to achieve a narrow distribution of the mixture of alkoxylate products. The medium containing the calcium catalyst may also influence whether the resulting modified calcium catalyst is able to form the desired narrow distribution of alkoxylation products. If the medium consists of a substance with a low dielectric constant as the main component, i.e. the solvent, the acid may form a separate liquid phase;
Great difficulties may be observed in obtaining a homogeneous mixture. On the other hand, for overly polar solvents, the organic moiety associated with the calcium atom may displace the solvent. Excess water is therefore typically avoided during modification of calcium-containing compositions. Most often the medium and the organic compound providing the moiety on the calcium atom are the same. Particularly advantageous media include ethylene glycol, propylene glycol, diethylene glycol, glycerin, butanediol, 1,3-propanediol, and the like. Conveniently, the medium used is
If it is not intended to be a reactant to produce an alkoxylate, it should have a sufficiently low boiling point that it can be easily removed from the catalyst and organic compound reactant mixture by distillation. Most often, the medium consists of a solvent having at least two heteroatoms, such as the active agents described herein. The acid is preferably added while vigorously stirring the calcium-containing composition to avoid excessive formation of neutralized salts. In this connection, it is preferred to add the acid gradually to the calcium-containing composition. Generally, no more than 10% of the acid to be added is added to the calcium-containing composition at any one time. Addition of acid is carried out at a convenient temperature, e.g. about 10°C
It can be carried out at a temperature of from about 50°C to 160°C, so to speak, from about 50°C to 150°C. Preferably a nitrogen atmosphere is advantageous. Calcium-containing compositions having at least one substituent having the formula -( ^HR3H ) can be prepared in any suitable manner. For example, the metal, hydride or acetylide of calcium can be reacted with an organic compound of the formula HXR ³ H having an active hydrogen atom. For compounds with higher molecular weights, e.g. 4 carbons or more, the formula
Lower molecular weight and more reactive and volatile compounds with HXR ³ H (e.g. those with 1 to 3 carbons, especially ethanol,
It is generally preferred to use compounds such as ethylamine, ethylene glycol, etc.) and then replace the substituent with a higher molecular weight substituent while removing the lower molecular weight material by evaporation. Alternatively, the calcium-containing composition can be made from quicklime or slaked lime by the methods disclosed later herein. Compounds with the formula HXR ³ H include those organic compounds with active hydrogen described with respect to the alkoxylation products of the invention, such as alcohols, phenols, carboxylic acids and amines. Most often the compound with the formula HXR ³ H is an alcohol. If an exchange reaction is to be performed to provide a higher molecular weight substituent on the calcium atom, acid modification is performed prior to exchange and a lower molecular weight material is used as the exchange substituent to enhance the acid modification process. It is generally preferred to do so. Preparation of substituted calcium catalyst compositions from calcium metal, hydrides or acetylides is typically performed at elevated temperatures, e.g.
Carry out in a liquid medium at 200°C or above.
The organic compound making the substitution usually provides the excess of the compound required to react with the calcium reactant. For this reason, the weight ratio of calcium to organic compound is often in the range of about 0.01:100 to 25:100. The reaction can optionally be carried out in the presence of an inert liquid solvent. The exchange reaction is also carried out at elevated temperature and optionally under reduced pressure,
Facilitates removal of volatile components. The temperature is about 50°C to 250°C, for example about 80°C to 200°C or
Temperatures can range up to 250°C and pressures often range from 1 mbar to 5 bar, such as from about 10 mbar to 2 bar. It is generally preferred that the organic substituents on the modified calcium-containing catalyst composition represent the "starter" component for the alkoxylation process. The starter component is an organic compound having at least one active hydrogen that reacts with the epoxide. The alkoxylation is carried out using a catalytically effective amount of calcium-containing catalyst, for example about 0.01 to 10, often about 0.5 to 5% by weight, based on the weight of the starter component. The catalysts substantially retain their activity during alkoxylation regardless of the amount of epoxide used. Thus, the amount of catalyst can be based on the amount of starter fed to the alkoxylation zone and not on the extent of alkoxylation that takes place. Moreover, the catalyst can be recovered from the reaction product (as it is a solid) and then reused.
Indeed, it has been found that the prepared (pre-used) catalyst can provide excellent products. The catalyst appears to be relatively storage stable and also relatively water resistant. Therefore, it can be stored under favorable conditions. Typically, the catalyst and starter components are mixed, the epoxide is added at the reaction temperature until the desired amount of epoxide has been added, the product is then neutralized, and then, if desired, any residual components are removed from the product mixture. stripping of reaction starter material,
It can be terminated with any procedure including filtration or further reaction to produce the sulfate salt, for example. The temperature of alkoxylation is sufficient to provide suitable reaction rates without degrading the reaction or reaction products. Often the temperature is around 50
and 270°C, such as from about 100°C to 200°C. Pressurized reactors are preferably used when low boiling epoxides such as ethylene oxide or propylene oxide are used, although the pressure can also vary widely. The alkoxylation reaction medium is preferably agitated to ensure good dispersion of the reactants and catalyst throughout the reaction medium. Also, the epoxide is usually added at a rate close to the rate at which it can react. Typically, according to the process of the invention, the alkoxylation product is neutralized immediately after removal of the catalyst used, but the mixture of alkoxylation products is relatively neutral (independent of the PH of the catalyst-containing product). For example about PH
6). However, neutralization aids in recovery of the catalyst from the alkoxylation product mixture. During neutralization, acids that tend to form catalyst-containing gel structures or solids that clog the filtration apparatus should be avoided. Sulfuric acid, phosphoric acid, propionic acid, benzoic acid, etc. are conveniently used. Preparation of Catalysts from Lime The present invention describes catalyst species active in the alkoxylation of organic compounds having at least one active hydrogen, such as alcohols, especially long-chain fatty alcohols, carboxylic acids, amines, polyols and phenols. A procedure is provided that can effectively use calcium oxide (quicklime) and its hydrated form calcium hydroxide (slaked lime) (both referred to herein as "lime") to produce slaked lime. This is accomplished by the following general procedure. The lime is first contacted with the activator ethylene glycol under conditions such that the lime and the activator react or interact to form one or more catalytically active derivatives, hereinafter properly referred to as "derivatives". let Derivatives of this reaction are particularly effective in the alkoxylation of alcohols, especially primary alcohols such as long-chain fatty alcohols or mixtures thereof, and are used as starters in the production of nonionic surfactants. However, the derivatives can also be used effectively in the catalysis of a wide variety of organic compounds having active hydrogen. The activator derivatives of ethylene glycol readily catalyze the alkoxylation of ethylene glycol itself in situ, thereby starting from ethylene glycol with any desired nominal molecular weight and advantageously a relatively narrow molecular weight distribution. Poly(alkylene glycols) can be produced. As another example, if the activator is monoethyl ether of ethylene glycol (MEEG),
If the derivative is alkoxylated directly with ethylene oxide, the product will be a mixture of ethoxylates of MEEG, the composition of which will be determined by the molar ratio of ethylene oxide to MEEG. As used herein, the term "excess active agent" refers to the amount of active agent that does not chemically or physically combine with calcium and thus can be removed by simple physical means. The technique used for this operation is not critical. Although vacuum stripping is recommended for its simplicity and efficiency, evaporation and other procedures may also be used. The derivative is obtained in slurry form as a finely divided, finely divided solid that can be easily separated from the reaction mixture by filtration, decantation, or similar procedures. The products thus obtained are catalytically active in alkoxylation reactions with or without acid modification. It is a particularly desirable feature that the catalyst can be used to provide alkoxylate surfactants with characteristically narrow molecular weight distributions, low pour points, and low levels of unreacted starter components. In this method of use, the alcohol exchange (also referred to as alkoxide exchange) reaction is carried out by contacting the catalyst and a starter component, such as an alcohol, under conditions that cause the reaction to occur. A portion of the starter alcohol is thus present as the alcoholate of calcium, which is itself the active species for the alkoxylation reaction. This reaction mixture is then reacted with one or more epoxides, such as alkylene oxides such as ethylene oxide, by known procedures to produce the desired surfactant. As the lime is solubilized, the alkalinity of the medium increases; the "accumulation" of alkalinity can therefore be used as a screening method to identify potentially useful active agents. In this test, calculated as CaO, based on 5 g of calcium charged (calculated as CaO), as determined by titration with 0.01NHCl (alcoholic HCl) in ethanol, as described in more detail below. Approximately 1
g or more should be sought. Step 1: Catalyst Preparation In the first step of the process of the invention, CaO and/or Ca(OH) ₂ are mixed with an activator to form one or more derivative species as described above. The purpose of this treatment is to solubilize enough lime to be catalytically effective in the alkoxylation reaction;
The lime concentration can therefore be either below or above its maximum solubility in the activator, provided only that enough lime is solubilized to be catalytically effective. However, as a general guideline, the concentration of lime used in the first step is typically about 1 to 2
Should be between %. Although lime should normally be present in slight excess of its solubility in the activator, lime concentrations in excess of about 30% are rarely desirable. The temperature for this procedure is not believed to be critical and can range from about 50°C to well above the boiling point of the activator, typically 200°C.
about 90 to 150°C, preferably about 125 to 150°C
It is preferable to operate in the range of 100 to 1000 ml, and the system can be placed under reduced or increased pressure to maintain any desired temperature while keeping the active agent in the liquid phase. Conveniently the temperature and pressure conditions are such that water is evaporated and removed from the reaction medium. Preferably, the preparation of the catalyst is carried out under a substantially inert atmosphere, such as a nitrogen atmosphere. To carry out the first step of the method, simply place the lime in an agitated vessel with sufficient agitation to form a lime slurry and for a suitable period of time to solubilize at least a portion of the lime. Add to the activator. This is usually completed within about 1 to 4 hours. The amount of lime solubilized is, of course, related to the concentration of lime present, the effectiveness of the activator used, and the temperature, time and agitation employed. Ideally, the desired amount of lime is solubilized for the sequential alkoxylation reaction. Sources of lime for this process include any commercial grade quicklime or slaked lime. This is because the impurities typically contained in such lime do not significantly adversely affect the catalyst formed by the procedure of the present invention. The resulting lime/activator derivative is suitable for direct use as a catalyst in alkoxylation reactions (although acid modification is preferred to enhance the narrowness of the alkoxylation product). This is the case, for example, when ethylene oxide should be added to ethylene glycol as an activator in order to produce polyethylene glycol with any desired molecular weight. If a catalyst is to be used to produce a surfactant or other alkoxylation product using a different starter, an exchange can be made as described above. For example, in preparing surfactants, surfactant range alcohols or such alcohols, typically from C ₁₂ to
The lime/activator derivative can be added to a stirred vessel containing a mixture of _C14 alcohols. The concentration of the derivative used can vary over a very wide range, but conceptually it is approximately the desired concentration for sequential ethoxylation reactions. The concentration during the exchange reaction can be any temperature at which the reaction occurs, but is preferably in the range of about 200-250°C, and the pressure can be adjusted to achieve this temperature. If an exchange procedure is to follow, the activator selected is preferably above about 200°C so that it can be easily stripped from the detergent alcohol, which mostly boils at 250°C or higher. It should also have a low boiling point. The resulting alcohol exchange product is suitable for use directly as a catalyst in alkoxylation reactions to produce surfactants starting with exchange alcohols or alcohols. However, it is preferred that the alcohol exchange product is acid modified to enhance the narrowness of the alkoxylation product. Catalysts produced by the above methods often exist in the form of stable slurries of finely divided (e.g. about 5 micron) particles, strongly basic (PH about 11-12), and containing excess CaO. . Step 2: Acid modification of the lime-derived catalyst Although not necessary for the alkoxylation reaction,
If a narrower distribution of the alkoxylation product is desired, the lime/activator derivative or its alcohol exchanged product is partially neutralized with an acid prior to use as a catalyst for the alkoxylation. is highly preferred. Although the exact chemistry of this procedure is not well understood, it does provide a demonstrable improvement to the overall procedure in that the molecular weight distribution is narrowed even further. Additionally, acid-modified catalysts tend to require little or no induction period in alkoxylation reactions, yet also increase the reaction rate over that of their unmodified counterparts. In contrast, addition of acid to conventional catalysts such as calcium hydroxide slows down the alkoxylation rate while not producing any beneficial effect on product distribution. Useful acids are polyhydric oxyacids of elements of Groups A and B, Groups A and B, and Group B, in which the oxyanion has a valency greater than one. Preferred oxyacids are sulfuric acid, phosphoric acid and molybdic acid and tungstic acid; among these sulfuric acid is particularly preferred. The acid added may be in concentrated or diluted form, but concentrated form is preferred to minimize the amount of water present. The acid can be added to the catalytically active reaction mixture at any time prior to alkoxylation and then briefly stirred to gradually form a reaction mixture slurry. Although the acid can be added under any prevailing ambient conditions, it is preferred to cool the slurry to 75°C or less prior to adding the acid. Neutralization often occurs without significantly affecting the physical properties of the slurry. Often about 20 to 90%, such as about 25 to about 75%, and sometimes about 40 to about 60% of the titratable alkalinity of the slurry is neutralized. Higher degrees of neutralization can be employed but care should be taken not to form a complete calcium salt of the oxyanion. In no case should more acid be used than there are equivalents of lime available to react with the acid. Advantageous results can be obtained if the catalyst is used in its "crude" form, ie without separation from the reaction mixture or purification.
Nevertheless, the lime/activator derivative, with or without acid modification, can be separated from the reaction mixture, purified, dried and then stored, if desired. An operation such as that described above involves stripping off excess activator or other organic material with active hydrogen, filtering the resulting slurry, reslurriing the wet solids with a solvent (e.g., tetrahydrofuran), and then refiltering. This can be carried out in a straight-line manner, such as by drying and then preferably drying under reduced pressure. Although the solids thus obtained are catalytically active, they are often
The activity is substantially less than that of the catalyst in the form of a catalyst. However, despite the reaction rate, the desired narrow molecular weight distribution and other advantages can still be obtained. It is a highly desirable and entirely unexpected aspect of this aspect of the invention that the overall process embodied in the various procedures described above for producing catalyst from lime is highly "tolerant" of process variation. This is an advantage. Thus, as already indicated, the acid is added, yet within reasonable limits there is considerable flexibility in how much acid to use. Likewise, unreacted activator can be removed in whole or in part, for example prior to an exchange reaction, if employed, or it can remain present during the exchange reaction. Furthermore, the catalyst can be reused indefinitely, used and stored in its "crude" form, or purified and dried, with any loss in reaction rate being compensated for by increasing the temperature. Next, the procedure for producing a nonionic surfactant will be described for reference. An embodiment of this method includes:
Illustrated by the following generalized procedure for the preparation of a slurry of calcium alkoxylation catalyst intended for use in the preparation of "peaked" (narrow molecular weight distribution) linear alcohol ethoxylates (nonionic surfactants) be able to. When applied to the specific case of producing nonionic surfactants, the process of the invention is characterized by a considerable degree of operating latitude. This is true in preferred process formats that produce acid-modified forms of the catalyst. In terms of the chemistry that occurs, there are two separate steps in the preparation of non-reformed catalysts and three separate steps in the preparation of acid-reformed catalysts. Steps 1 and 2, which are common to both catalyst types, involve the following reactions: Step 1 - Lime (or a mixture of a major amount of lime and a minor amount of other alkaline earth base) and a suitable activator. reaction. Step 2 - Reaction of the product produced in step 1 above with an alcohol of the detergent range to effect an exchange of organic groups derived from the activator for organic groups derived from the alcohol of the detergent range. During or after the exchange reaction of step 2, the activator, which is preferably substantially more volatile than the detergent range alcohol, is removed from the system by distillation. At the end of this operation, the unmodified catalyst is obtained in the form of an activator-free slurry in detergent range alcohol. In the preparation of the unmodified form of the calcium catalyst, steps 1 and 2 above can be combined into one operation, in which the lime is reacted with a mixture of an activator and an alcohol in the detergent range. If particularly effective activators are used (e.g. ethylene glycol, 1,2-propylene glycol, ethylene glycol monoethyl ether, etc.), a separate procedure combining the activator with a detergent-range alcohol is often preferred. . This is because it minimizes color build-up in the catalyst slurry. Both procedures are equally acceptable from the point of view of the properties of the final product. A modified method in which the activator is provided in a slurry of detergent range alcohol and calcium base, or the detergent range alcohol is provided in a slurry (or in some cases a solution) of calcium base in the activator. Although both are operationally viable, their use has not been shown to provide any advantage over batch-feeding formats. The production of acid reforming catalysts involves a third major processing operation, which, like steps 1 and 2, is a separate step from the standpoint of the chemistry that occurs. Step 3 - Certain suitable polyoxyacids (e.g.
Treatment of unreformed catalysts in detergent range alcohols deficient in H ₂ SO ₄ , H ₃ PO ₄ , H ₂ MoO ₄ , etc.). This process provides a highly active acid reforming catalyst in the form of a slurry in detergent range alcohol. Water is believed to be produced as a by-product of this partial neutralization reaction; therefore, the product slurry is usually vacuum-treated before use in the ethoxylation reaction for the production of nonionic surfactants. Subject to drying operation. The acid modifier charge can be based on the initial lime charge or, even more preferably if possible, the lime/activator using 0.01N alcoholic HCl in the presence of bromothymol blue indicator. It can either be based on the "active catalyst" value obtained by titrating the reaction mixture for alkalinity content. A particularly advantageous procedure is to follow the course of the lime/activator reaction by titration and to base the charge of acid modifier on the alkalinity value obtained when a certain level of alkalinity is reached. It is. A particularly convenient and effective procedure is, for example, to add acid modifiers at a level of about 50% of this "constant" alkalinity value. Monitoring the lime/activator reaction by titration and ultimately determining the acid modifier charge based on this analysis is often the preferred procedure, but the procedure should not be used with amino-functional activators. I can't. This is because amine functionality interferes with alkalinity analysis. In such cases, the preferred procedure is to base the acid modifier charge on the alkalinity obtained by titrating an activator-free (stripped) slurry of catalyst in detergent alcohol. Acid modifiers are often optionally added at or during the lime/activator reaction, at or during the activator stripping operation, at the end of the activator stripping operation, or during the alkoxylation reaction itself. It can be added just before starting. In the case of amino-functional activators, of course, the modifier cannot be added until all of the activator has been removed from the slurry. GENERAL PROCEDURES FOR PROCESS OPERATIONS Because the method affords such wide operational latitude as described above, no single procedure can be said to represent a "general procedure." Despite this idea, one procedure sufficient to illustrate the method is the format used to make a number of formulations summarized in the table. Lime (commercially available or calcined for 6 hours at 600°C) and 2-ethoxyethanol (obtained from Union Carbide) were placed in a reflux condenser, thermocouple,
A 10-tray distillation column and an appropriately sized agitated vessel equipped with an inert gas purge inlet were charged. Reactant is 2-ethoxyethanol 60 to 80
The weight ratios ranged from 1 part to 1 part lime. The charge was heated to reflux temperature (approx.
135°C) for 2 to 6 hours,
During this time, the refluxing solvent is removed from the overhead distillate at a make rate slow enough so that only about 10 to 15% of the raw solvent charge is removed from the overhead distillate during the total reaction time. continuously or intermittently from the overhead distillate. The purpose of this operation is to remove water from the system, either introduced with the reactants or produced by the chemical reaction. The countermixture was sampled at periodic intervals during the reflux period to monitor alkalinity build-up. Accumulation of alkalinity indicates the formation of catalytically active substances. The analytical method employed for this purpose is titration with 0.01 NHCl in 2-ethoxyethanol using a promothymol blue indicator. The lime/activator reaction step is considered complete if two consecutive titrations yield similar "alkalinity" levels. The normal time to reach this point is about 4 hours under the typical conditions of the experiments shown in the table. At this point, the reaction mixture is diluted with detergent range alcohol for ethoxylation; typically the amount of alcohol added is approximately 100 g/g of lime (calculated as CaO) used in the first reaction.
It is. The resulting mixture is cooled to about 75°C and then treated with sufficient acid modifier, preferably sulfuric acid or phosphoric acid, with stirring to determine the presence of the lime/activator mixture by a final titration performed on the lime/activator mixture. Neutralizes approximately 50% (on an equivalent basis) of the indicated alkalinity. The temperature is then increased to remove the activator from the reaction mixture by distillation at atmospheric pressure. Distillation at atmospheric pressure is continued until the kettle temperature reaches about 175-180°C. At this point, the pressure in the system is approximately
180 mmHg and stripping of the activator until the kettle reaches a temperature of about 215 to 225°C and both the kettle product and distillate are active as shown by gas chromatography (GC) analysis. until it no longer contains the agent (e.g. 1000 wt.
ppm or less, often less than 100 ppm by weight). The activator-free catalyst slurry thus obtained in detergent alcohol can be used directly as feed to the ethoxylation reactor or optionally diluted with sufficient dry detergent range alcohol. Either can be used to achieve any desired concentration in the slurry. The final "alkalinity" value for this slurry can be obtained, if desired, by the same titration procedure described above. The above procedure represents only one of many equally possible forms of the method. The experiments summarized in the table illustrate several, but by no means all, uses of the format possible with the various combinations that can be obtained in the various process steps. EXAMPLES The invention is further illustrated by the following examples. The examples do not in any way limit the applicability and scope of the present invention. Example 1 Using the general procedure described above under various reaction conditions to prepare 1-dodecanol or two commercially available _C12 ~
Specific ionic surfactants were produced that were "started" with one of a mixture of C ₁₄ linear fatty alcohols. The data for these experiments are detailed in the table. In the table, "Alfol 1214" and "Lorol" 1214 are C ₁₂ and
A mixture of _C14 alcohols, each named Conco from Lake Charles, Louisiana.
It is commercially available from Henkel & Co., Germany, Germany. MEEG (available as Cellosolve™ solvent from Union Carbide, Danbury, CT) was used as the activator. In some experiments, marked by stars in the CaO column, the CaO was calcined to drive off all water. MEEG was removed by stripping (eg, to <100 ppm by weight) prior to ethoxylation in all experiments. In some experiments the H ₂ SO ₄ modifier was added prior to stripping off the activator and in some experiments after stripping. Experiment 23 (control example)
illustrates the use of metallic potassium alcoholates as catalysts. These data indicate a narrow molecular weight distribution,
This demonstrates the remarkable flexibility of operating conditions possible for the process of the invention while still producing products with excellent overall properties and low levels of unreacted residual alcohol.

【table】

【table】

[Table] Theoretical values

Main peak 18.7 19.7 21.5
20.7 18.6 17.1
27.6
area%

Unreacted Al − − −
− 1.71 1.43 −

call%

(weight)

【table】

[Table] Example 2 As shown above, the preferred procedure of the present invention is (a)
activator used alone in the initial reaction with CaO, (b) H ₂ SO ₄ as a modifier, (c) acid modifier added prior to removal of the activator, and (d) reflux time. "Activity" measured by the above titration at the end point of
Use an amount of acid, which is 50% of the CaO content. Using this format of the process of the invention, a series of surfactants were prepared by sequential ethoxylation. In this case, a single reactor charge was used and a portion of the reactor contents was removed each time the desired ethoxylation level was reached. Data for these experiments are shown in the table.

【table】

[Table] Weight%

Example 3 A further series of sequential ethoxylation experiments were conducted in a full-scale production facility. The data for these experiments are summarized in the table. In this table, “Ca”
indicates a catalyst derived from CaO, “K” is KOH
A control experiment using a catalyst is shown. These data demonstrate that the CaO-derived catalyst produced a significantly narrower molecular weight distribution than the KOH catalyst, as evidenced by the large predominant GC peak found in the ethoxylate produced by the CaO catalyst. be observed. Furthermore, the residual alcohol content was substantially lower for the CaO catalyzed product. The products of Experiments 2, 3 and 7 were analyzed by capillary gas chromatography and the following compositions were determined (±10% error based on response factors for each species):

【table】

【table】

【table】

[Table] Established.
Example 4 As mentioned above, the catalyst of the present invention can not only be used in its "crude" form as in the previous examples, but also can be recovered and purified before use.
This example illustrates the properties and use of a CaO-derived catalyst isolated, purified, and dried according to the techniques previously described. The table shows key data for experiments using acid reforming catalysts versus experiments using non-reforming catalysts. For comparison, suitable data are given for a conventional potassium catalyst prepared by reacting calcium metal with 1-dodecanol. The latter catalyst was a homogeneous catalyst system and no attempt was made to isolate the active catalyst species. The dry CaO catalyst is obtained as yellow, granular (rather agglomerated) fine particles and is required to yield a po-sitive test for alkalinity.
It was too insoluble in MEEG1214 or Alfor1214. In fact, these solids are present in Alfor 1214, which is added during the slurry preparation step.
This also formed such a poor slurry that no positive test for alkalinity was observed. (A "poor" slurry means that the solids were not able to be properly suspended, ie, the slurry was unstable and settled within 1 or 2 hours). Characterization of these solids by reflectance IR, powder X-ray, and microanalysis shows that they are X-ray amorphous, some long-chain organics are present, and sulfur is present in the acid-modified species. It was shown that there was a small amount of unreacted CaO and Ca(OH) ₂ present. Both solids have low activity, despite their presence in quite substantial concentrations in the reactor feed, as shown by the ethoxylation rate data presented in the table. Although the unreformed catalyst is present in higher concentrations than its acid-modified counterpart,
There was poor activity at 140°C, so the reactor temperature was increased to 160°C to carry out the reaction. The low level of activity exhibited by the two CaO-based catalysts can be attributed to the very poor nature of the Arphor 1214 slurry obtained with isolated catalyst species. For experiment 2, a less than optimal preparation procedure (CaO was mixed with MEEG and alcohol 1214 instead of MEEG alone)
The intentional use of (heated with mixtures with) also probably contributed to the relatively low catalytic activity.
Under the preferred preparation conditions, where the catalyst is not isolated, activity levels 3 to 6 times higher than those observed in the studies in this invention are expected. In the table, the rate of 7.1 g/min shown for the potassium catalyzed (control) experiment at 140°C in the special annular reactor used to produce the data of these examples. This is a typical value for KOH catalysis. Thus, mechanical factors may be diminished as a possible cause for the relatively low activity obtained with isolated calcium catalysts. Although isolated catalysts derived from CaO exhibit lower activity, their performance characteristics are otherwise difficult to distinguish from those of their non-isolated counterparts. That is, although both CaO-based catalysts produce ethoxylates with a narrower molecular weight distribution than the potassium control catalyst, the acid-modified catalyst is only more active than its unmodified counterpart. The acid reforming catalyst is much more selective, as judged by comparison of the molecular weight distribution pattern) (the acid reforming catalyst is much narrower).

【table】

Table: Example 5 This example graphically illustrates the narrowed molecular weight distribution achieved by the method of the invention. Figure 1 shows a typical CaO catalyst prepared using ethylene glycol, acid-modified ethylene glycol (indicated by "H ⁺ "), MEEG acid-modified ethylenediamine (EDA), and monoethanolamine (MEA) activated CaO catalyst. Typical molecular weight distributions for nominal 6 mole ethoxylates of 1-dodecanol are shown, all compared to a metallic potassium control (prior art). Figure 2 provides a similar comparison and shows CaO and CaO using ethylene glycol as the activator.
(OH) ₂ to demonstrate practical equivalence in terms of performance. It is a significant advantage of the present invention that the present invention is substantially insensitive to moisture present prior to alkoxylation, since any contained or environmental moisture converts CaO to Ca(OH) ₂ . Figure 3 illustrates the ethoxylation of a mixed surfactant grade alcohol (Alfor 1214) using a CaO catalyst activated with ethylene glycol ("EG"). Figure 4 shows the unmodified and
The use of both MEEG-activated CaO modified with either H ₃ PO ₄ or H ₂ SO ₄ is shown. The ethoxylate distributions shown in Figures 1-4 were determined using gas chromatography using a column packed with 2% OV-1 on Chromasorb W™ packing. The temperature limit of the column is such that little accuracy is achieved with ethoxylates having eight or more oxyethylene groups. Example 6 Three batches of CaO and activator (monoethylene glycol) were prepared as follows: Batch A: A mixing tank containing about 22.500 pounds of monoethylene glycol was heated with nitrogen for about 1 hour. , sparged at 45° to 50°C.
The mixing tank was continuously agitated by a jet nozzle at the base of the tank and a spray ring at the top of the tank. Approximately 375 pounds (170 Kg) of lime (CaO) was added to the mixing tank while the mixing tank was maintained under a vacuum of 500 mm Hg (about 0.34 atmospheres absolute) for half an hour. The temperature of the fluid in the tank increased from approximately 48°C to 59°C during lime addition. The mixing tank was then heated to about 118°C (it took about 1.5 hours to achieve this temperature) and then heated to about 118°C to
A temperature of 130°C was maintained for 3 hours. 3 per mole of a dispersant, i.e. a mixture of linear alcohols having 12 to 14 carbons and the alcohol (available as TELGITOL(TM) 24-L-3 (cmw) surfactant from Union Carbide). About 400 pounds (182 Kg) of a surfactant made from moles of ethylene oxide were added over a 1.5 hour period during which time the temperature in the mixing tank decreased from about 127°C to about 110°C. Dispersant addition was started after 1 hour and 37,500 pounds of alcohol (Alphor 1214) was added. Addition of the alcohol took about 1 hour, during which time the temperature of the mixture was about 90°C. A two-phase mixture formed upon addition of the alcohol and remained throughout the remainder of the batch's manufacture. mixing the mixture continuously for an additional 1.5 hours;
Approximately 250 pounds of concentrated sulfuric acid (114
Kg) was added. The mixture after addition of acid is approximately
Mixing continued for 6.5 hours and then pumped to a charge tank for later use. Each dispersant, alcohol and acid, was added through a spray ring at the top of the mixing tank. Batch B: Used the same mixing tank as above except only the bottom nozzle was used for the mixture, and used 22,500 lbs.
A charge of 375 lbs (175 kg) of lime (CaO) was purged with nitrogen for 1 hour at approximately 45-50°C.
Kg) was added in 50 pound (23 Kg) portions as in Batch A under reduced pressure over half an hour. During this time the temperature rose to approximately 62°C.
It takes approximately 1.75 hours to heat the mixing tank to 116°C, and then the tank is heated to approximately 116°C to 130°C.
It was kept for 2.5 hours. Tergitol (trademark) 24−
Approximately 400 pounds (182Kg) of L-3 surfactant at 0.75
Added over time. Approximately 0.75 of dispersant addition
After an hour, 250 pounds (114 Kg) of concentrated sulfuric acid was added over a one hour period. Mixing continued for approximately 2.5 hours and the reaction mixture, a single liquid phase slurry, was pumped to a circulation reservoir for subsequent use. Batch C: Using 400 pounds (182Kg) of lime, the temperature of the ethylene glycol at the beginning of lime addition is about 39°C, the temperature rises to about 53°C, and using 300 pounds (136Kg) of concentrated sulfuric acid. The procedure and equipment described for the preparation of Batch B was substantially repeated, except that after the acid addition was complete, the mixture was held at 90° C. for 3 hours before being transported to a storage tank. After preparing these batches, batches B and C
were mixed together for approximately 20 hours. Alfor 1214 alcohol was added to the lime as the mixture of batches B and C was pumped to the distillation column. The distillation column has a spacing of 20 inches (50 cm) and a nominal diameter of 6
24 valves (unsealed) with feet (1.8m)
Has a tray. The rate of addition of alcohol was sufficient to give a weight ratio of alcohol to ethylene glycol of 5:3. The distillation column is fed to the top tray of the column (approximately 7000 to 9000 g/hr).
(3200 to 4000 Kg/hour)) was operated as a stripping tower. Approximately 33 to 35mm
The temperature at the top of the column at Hg absolute pressure is about 114°C to 116°C and at the base about 205°C to 215°C.
It was hot. Steam flow to the base was approximately 6000 to 7000 pounds per hour (2700 to 3200 kg per hour). Residual oil was periodically removed by the liquid level of the column. The production rate of overhead distillate is 3000 to 3000 per hour.
It was 5,000 pounds (1,400 to 2,200 kg/hour). Then batch A (with some additional alcohol)
1214 in a weight ratio of 5:3) was passed through a distillation column. The residual oil slurry from the batch was collected and stored in a circulation tank under nitrogen atmosphere. Additional Alfor 1214 was added to the slurry to give a concentration of catalyst (calculated as CaO) of 1.0% by weight. Analysis of this slurry revealed that ethylene glycol was approximately 0.1
% by weight, and it is clear that the stripping of ethylene glycol is not complete (less than 0.05% by weight of ethylene glycol is preferred). This slurry, or masterbatch catalyst, acts as a catalyst for a series of ethoxylations of alcohol 1214 with ethylene oxide at 140° C. and 1500 atmospheres gauge pressure. The ethoxylation reactor has a capacity of 15,000 gallons and is nitrogen inverted.
It was a reactor. A slurry of starter and catalyst (0.1% by weight catalyst based on starter) was heated to 120° C. prior to starting the ethylene oxide flow. The ethylene oxide feed rate is initially approximately 3000 lbs/hour (1364 Kg/hr) and then increased to 9000 lb/hr (4091 Kg/hr) until approximately 100,000 lbs (45,454 Kg) of ethoxylate is present in the reactor.
Kg). The remaining ethylene oxide was allowed to react by keeping the mixture at 140° C. for 1 hour. using sulfuric or phosphoric acid,
The filtered product was neutralized. Details of the experiment are shown in the table.

【table】

Table: Example 7 This example illustrates a procedure for producing triethylene glycol (TEG) and tetraethylene glycol (TETEG) from ethylene glycol (EG). The following general procedure was used for the experiment. Calcium-containing catalyst at a temperature of 150℃ and about 180-200mmHg
was prepared over a period of 4 hours with continuous gradual removal of the ethylene glycol overhead distillate. Concentrated acids were used for the modification and were added after the catalyst was mixed with the ethylene glycol for the ethoxylation (post-addition), except as indicated in other embodiments. The ethoxylation was carried out in a 2 gallon capacity circulation reactor at about 140°C and 60 to 65 pounds per square inch (about 4 atmospheres gauge). The molar ratio of ethylene oxide to ethylene glycol was 2.3:1. The charge to the reactor was approximately 500 g of ethylene glycol mixture.
The product was neutralized with phosphoric acid at 80°C and passed hot through a Filter-Cal™ diatomaceous earth filter. Packed column [Chromasorb W (trademark) on packing]
Molecular weight distribution (area %) was determined by gas chromatography using 2% of OV-1] and samples were derivatized by reaction with Regisil™ silane obtained from Regis Chemical. did. Details are shown in the table. In the table, DEG represents diethylene glycol;
PENTEG stands for pentyl ethylene glycol; HEXAEG stands for hexaethylene glycol. Example 8 This example describes a procedure for producing triethylene glycol and tetraethylene glycol from diethylene glycol. The same general procedure as described in Example 7 was used except that the catalyst activator was diethylene glycol and the pressure during catalyst preparation was 40 mm Hg. The molar ratio of ethylene glycol to diethylene glycol was approximately 1.3:1. Details are shown in the table.

【table】

[Table] Means tsuttata.
b. Non-standard experiment because acid modifier was added to the reaction system in advance.
c. KOH pellets, 85% purity.
d. Laboratory reagent acid, ~85% concentration.
e. Crystals in dihydrate form.
f. MoO ₃ forms or 85% molybutenic acid.

[Table] It means something.
b. Non-standard experiment as acid modifier was added in advance.
c. Non-standard experiment because the amount of CaO catalyst charged was 2.0g instead of 1.0g.