JPH03229639A - Alkoxylation using modified calcium-containing catalyst - Google Patents

Abstract

PURPOSE: To prepare an alkoxylating catalyst by mixing calcium metal or a calcium-contg. compd. with an activator having a specified compsn. and reacting the produced compsn. with an oxyacid or a multi-valent metallic salt under specified conditions. CONSTITUTION: Calcium metal or a calcium-contg. compd. is mixed with an activator expressed by the formula I (X and Y denote each oxygen, nitrogen, sulfur or phosphorus, (a) and (b) denote each an integer which satisfies a valency requirement, Q is an electrically positive or neutral org. group corresponding to X or Y, Z and Z' denote each hydrogen or an org. group which does not interfere reaction or solubilization), to make react or dissolve at least partly and obtain a calcium-contg. compsn. having a titration alkalinity. The compsn. is reacted with one or more di-valent or multi-valent metallic salt of oxyacid under specified conditions, to prepare an alkoxylating catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the use of modified calcium-containing catalysts and alkoxylation products, such as condensation reaction products of alkylene oxides, in the production of organic compounds having at least one active hydrogen. 9 Another aspect of the invention relates to the use of a catalyst, comprising a calcium metal or a calcium-containing compound as a source for catalytically active calcium, such as calcium oxide or calcium hydroxide, and at least one oxyacid as a modifier. The present invention provides a method for producing modified calcium-containing catalysts for alkoxylation using divalent or polyvalent metal salts. Yet another aspect of the present invention is to provide a method for producing alkoxylated products having useful narrow molecular weight ranges using modified calcium-containing catalysts.

Sections 1 and 1 Various products such as surfactants, functional fluids, glycol ethers, polyols, etc. are produced by converting alkylene oxides into organic compounds having at least one active hydrogen, generally in the presence of an alkali or acid catalyst. It is commercially produced by a condensation reaction with The type and properties of the alkoxylation product depend, inter alia, on the active hydrogen compound, the alkylene oxide and the molar ratio of alkylene oxide to the organic compound used, as well as the catalyst. As a result of alkoxylation, the condensation product species (5pec-es)
mixtures are obtained with a range of molecular weights.

In many applications of alkoxylated products, some alkoxylated species exhibit much higher activity than others; therefore, it is desirable for the alkoxylation process to be selective for the production of those alkoxylated species. Furthermore, for many of these applications, mixtures of alkoxylated products within a narrow range of molecular weight distributions of the reacted alkylene oxides are superior to alkoxylated products dominated by a single alkoxylated species. For example, in surfactant compositions, the range of substances that require a surfactant to function typically varies. A range of alkoxylated species, although narrow in scope, improve the performance of the surfactant against a wide variety of substances that the surfactant may encounter. Additionally, mixtures of closely related alkoxylated species provide mixtures with other improved properties, such as with respect to cloud point, freezing point, pour point, and viscosity, compared to a single species. However, if there is an equilibrium and the distribution of species becomes too broad, not only will there be less of the desired alkoxylated species to dilute the mixture, but components that are more hydrophilic or lipophilic than those in the desired range will be detrimental to the desired properties. It could be profitable.

Furthermore, a wide range of alkoxylated species can limit the flexibility in the final product formation using the alkoxylated reaction products. It is often desirable to produce a product with a high concentration of m#I.

This concentrate can then be diluted with water at the time of use to save transportation costs and water storage. The ability to produce the desired concentrate typically requires large amounts of water, which would otherwise cause gelation (evidence of product instability) if heavier components are present. So,
It generally depends in part on having a narrow distribution of alkoxylated species.

It has long been recognized that a certain distribution of moles of alkylene oxide relative to moles of organic compound in the alkoxylation product is important.

For example, British Patent Specification No. 1.399,966 is disclosed for use in laundry detergents from about 10 to about 13. Discloses the use of ethoxylates with a hydrophilic-lipophilic balance (HLB) of 1. In order to obtain this HLB, it is stated that the number of moles of reacted ethylene oxide per mole of fatty acid is important. British patent specification Bancha 1,46
No. 2.133, the targeted cleaning composition used sufficient alkylene oxide cosurfactants to provide a very narrow HLB, ie, an HLB of about 10 to 12,5. British Patent Specification No. 1,462,134 discloses detergent compositions using ethoxylates having an HLB of about 9.5 to 11.5, preferably 10.0 to 11.1. has been done.

Thus, as the properties conferred by alkoxylated products become increasingly understood, there is a great need to adapt the manufacture of alkoxylated products to improve the desired properties. Efforts have therefore been made to provide alkoxylation products in which the distribution of reacted alkylene oxide units per mole of organic compound is limited to a range that improves the desired properties.

The alkoxylation process is characterized by a condensation reaction of at least one alkylene oxide with at least one organic compound containing at least one active hydrogen in the presence of a catalyst. The most common catalyst is probably potassium hydroxide. However, products prepared using potassium hydroxide generally exhibit a wide distribution of alkoxylate species, e.g.
H,J, 5chick, “
Nonionic surfactant (Nonionic 5urfac)
tants) J, 1 volume, Marcel Dezker (H
Arcel Dekker, Inc.) Sales, New York, pp. 28-41 (1967). Figure 6 of No. 223.164 shows the distribution of alkoxylate species produced by ethoxylating a fatty alcohol mixture with 60% by weight ethylene oxide using a potassium catalyst.

The distribution obtained in the alkoxylation process depends on the type of organic compound to be alkoxylated and can vary even when using homogeneous catalysts. For example, for nonylphenol, a Poisson-type distribution is Obtainable. However, decanol,
Regarding aliphatic alcohols such as dodecanol,
Distributions become wider. In this specification, these distributions are referred to as "traditional wide distributions."

Acidic catalysts can also be used. Although these catalysts tend to produce narrower and therefore more desirable molecular weight distributions, they also contribute to the formation of undesirable by-products and are therefore not widely used commercially.

Particular emphasis was placed on controlling the molecular weight distribution of the alkoxylation products. One attempt has been to strip unwanted alkoxylate species from product mixtures. For example, U.S. Pat. No. 3,682,849 describes a method for vapor phase removal of unreacted alcohol and low boiling ethoxylate components. is disclosed. The I/li composition each contains less than about 1% by weight of non-ethoxylated alcohols and monoethoxylates, less than 2% by weight of jetoxylates, and 3% by weight.
It is said to contain less than % by weight of 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 wide distribution of ethoxylate species. That is, there is still a significant amount of high molecular weight product present in the composition. According to the patent, in order to avoid the viscosity problems normally present with straight chain alcohols,
Approximately 20-30% of the starting alcohol is branched.

Obtaining a narrow distribution of alkoxylated species can be easily achieved at low molar ratios of epoxide reactant to organic compound. U.S. Patent No. 4,098°818 is patent! Disclosed are processes in which the molar ratio of (eg, alkali metals and alkali metal hydrides) to fatty alcohols is about 1=1. The ethoxylate distribution is disclosed as Parts C and D of Example 1 and is summarized as follows.

Primary Fatty Alcohols Part C Part D 12 Carbon Moles of 12 to 14 Carbons Product Molecular Weight Average Ethoxylation Distribution (%) 3.8 2.54 High catalyst content narrow with low alkylene oxide to alcohol ratio Low ethoxylation Seems to generate rate minutes. However, as the molar ratio of alkylene oxide to alcohol increases, the conventional wide distribution characteristic of alkali metal catalysts can be expected. Furthermore, even though the disclosed method reports that a narrow distribution of ethoxylate species is obtained, the distribution is skewed so that a significant amount of higher ethoxylates are present. For example, in Part C, 15% The above ethoxylate compositions have at least three more oxylene groups than the average based on the reactants, and the amount in Part D is 16% or more.

European Patent Application No. AOO95562, published on December 12, 1983, aims at high selectivity towards lower ethoxylate species as well as higher ethoxylate products when using low ratios of ethylene oxide reactant to alcohol. This example shows that it is possible to obtain the property that the selectivity disappears quickly when 0
For example, Example 1 reporting the use of diethylaluminum fluoride catalyst (described as 1 mole of EO adduct) used 300 g of a 12-14 carbon alcohol and 64 g of ethylene oxide; and Example 5 using the same catalyst (described as 1°5 mole EO adduct) according to the data shown in Figure 0 using a weight ratio of alcohol and ethylene oxide of 300:118. , the distribution appears to be as follows.

! JLLL 1 Dl Eo 27 10 El 50 36 E2 17 33 E3 4 16 From the 1 mole EO adduct described to the described 1,5 u/
Even with a slight increase in ethoxylation to &EO adducts, the distribution of ethoxylate species broadened considerably, producing more higher ethoxylates, as can be expected from the previously wide distribution. This may be because the catalyst is consumed during the reaction process and is therefore not available at high loading levels to obtain a narrowly distributed alkoxylated product mixture.

Several catalysts have been identified that have been reported to give higher ethoxylate molecular weight distributions that are narrower than expected from conventional broad distributions. In particular, this study highlighted that derivatives of Group IA alkaline earth metals are ethoxylation catalysts. The interest of these catalysts, which to date has been almost exclusively limited to the production of nonionic surfactants, is due to their narrower molecular weight distribution, lower unreacted alcohol content and What has happened is that they have been demonstrated to be able to provide hydrophobic ethoxylates with low pour points.

Recently, vang and co-workers have shown that comparable products produced by state-of-the-art catalytic reactions using alkali metal hydroxides have lower pour points, narrower molecular weight distributions, lower unreacted alcohol content and better Granted a series of U.S. patents that first described the use of unmodified or phenol-modified oxides and hydroxides of barium and strontium as ethoxylation catalysts to produce nonionic surfactants with excellent detergency. Ta. U.S. Patent No. 4.210
No. 764, No. 4.223.164, No. 4,239.
No. 917, No. 4,254.287, No. 4゜302.6
13 and 4,306.093. Importantly, these patents disclose that magnesium and calcium oxides and/or hydroxides can act as promoters for barium and strontium compounds. You can, but
They contain claims that they do not exhibit catalytic activity for ethoxylation (US Pat. No. 4,302,613).

Although the molecular weight distributions of the ethoxylates disclosed in these patents are narrower than conventional distributions, they do not appear to be narrow enough to meet 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 carbons and 60% ethylene oxide using various catalysts. A barium hydroxide catalyst is stated to provide a product mixture containing about 16% 6 mole ethoxylate as the predominant component. However, the distribution is still poor in that ethoxylate species with three or more oxyethylene groups than the most abundant component are about 19% or more by weight of the mixture, and the distribution is skewed toward higher ethoxylates. Relatively spacious. Experiments with strontium hydroxide catalysts, also shown in that figure, appear to have a more symmetrical distribution, although the most abundant component, 7 mole ethoxylate, is around 14.5% by weight.
and about 21% by weight of the composition had three or more oxyethylene groups than the most abundant component.

Also, US Pat. No. 4,239,917 discloses ethoxylate distribution using barium hydroxide catalysts and fatty alcohols. Figure 7 of that patent shows a distribution in which 4 mole-ethoxylate is the predominant component at a 40% ethoxylation level. Approximately 19% by weight of the mixture
These have three or more oxyethylene groups than the most abundant component. Figure 4 shows the ethoxylation distribution at a 65% ethoxylation level. 9 moles and 1
The 0 mole ethoxylates were the most abundant, each representing about 13% by weight of the composition. Although the distribution is relatively symmetrical, approximately 17! Importantly, a comparative example using sodium hydroxide is shown in each of these figures, with the amount % having at least 3 more oxyethylene groups than the average peak (9,5 oxyethylene groups) and lower We demonstrate peaking that can be achieved using conventional basic catalysts at ethoxylation levels but cannot be achieved at higher ethoxylation levels.

HcCain and co-workers have published a series of European patent applications describing the use of basic salts of alkaline earth metals, especially calcium, dissolved in the reaction medium as catalysts. These applications further disclose catalyst preparation procedures involving alcohol exchange between the alkoxy moieties of metal alkoxide catalyst species. European Patent Publications Nos. 0026544, 0026547 and 0, all of which are incorporated herein by reference.
See also US Patent Application No. 454.560 (Barium-Containing Catalysts), filed December 30, 1982. These researchers also disclose a method for promoting the catalytic action of certain alkaline earth metal derivatives by partially neutralizing them using strong acids. No. 4,453,022 and U.S. Pat. No. 4,453, both of which are herein incorporated by reference.
No. 023 (barium-containing catalysts), these researchers would also confirm Young's findings regarding calcium oxide. That is, Matsugain et al. teach that calcium oxide does not produce lower alkoxides when treated with ethanol.

In particular, calcium metal or calcium hydride is a typical starting material used by Matsugain et al. to produce calcium-containing catalysts.

However, these starting materials are expensive.

Therefore, there is a desire to use commonly found sources of calcium, such as calcium oxide (quicklime) and calcium hydroxide (slaked lime), to produce calcium-containing catalysts for alkoxylation. Furthermore, quicklime and slaked lime are by far the cheapest, most abundant, least toxic and the most environmentally acceptable of all alkaline earth metal derivatives.

The calcium-containing catalysts disclosed by Matsugain et al. provide improved selectivity to higher alkoxylate species compared to mixtures prepared using conventional potassium hydroxide catalysts; in fact, these calcium-containing catalysts do not contain strontium or barium There is reason to believe that it provides a narrower distribution of alkoxylates than that obtained with containing catalysts. However, there is still a narrow distribution, especially alkoxylated products in which at least one component constitutes at least 20% by weight of the composition and has more than three alkoxyl groups than the average peak alkoxylated component, only a small proportion of the product mixture. Further improvements are needed to provide alkoxylated products with a uniform distribution.

No. 621, currently pending, filed June 22, 1984, incorporated herein by reference.
, 991 relates to a method for producing alkoxylation mixtures with relatively narrow alkoxylation product distributions using modified calcium-containing catalysts. Also disclosed are methods of making alkoxylation catalysts using calcium oxide and/or calcium hydroxide as the source of catalytically active calcium. The alkoxylated product mixtures disclosed herein have a narrow, balanced distribution of alkoxylated species. These disclosed product mixtures contain significantly higher alkoxylated components, i.e., those with at least three more alkoxyl groups than the average peak alkoxylate species, which are not proportionate to large amounts, and have more than four fi-rich alkoxylated components. It is stated there that a narrow distribution can be obtained with alkoxy units of , ie in a region where conventional catalysts provide a relatively wide range of alkoxylated species.

No. 102, currently pending U.S. Patent Application No. 102, filed September 30, 1987, incorporated herein by reference.
．． No. 939 describes heterogeneous (organic polymer-supported) calcium-containing catalysts and their use in the preparation of alkoxylation products, i.e. condensation reaction products of alkylene oxides and organic compounds having at least one active hydrogen. Regarding. A method is provided for making heterogeneous (organic polymer-supported) calcium-containing catalysts for alkoxylation using oxidizing lucium and/or calcium hydroxide as the source of catalytically active calcium. Alkoxylation products are provided that have advantageous narrow molecular weight ranges, essentially neutral pH, and are free of catalyst residues.

i55jj The present invention provides a modified calcium-containing catalyst and a calcium metal or calcium-containing compound as a source for catalytically active calcium, such as calcium oxide or calcium hydroxide, and an organic or inorganic oxyhydroxide as a modifying agent. and at least one divalent or polyvalent metal salt of an acid.
The present invention further relates to a process for producing alkoxylated product mixtures having relatively narrow alkoxylated product distributions using modified calcium-containing catalysts.

The modified calcium-containing catalysts of the present invention are modified with at least one divalent or polyvalent metal salt of an organic or inorganic oxyacid, such as calcium sulfate, aluminum sulfate, zinc sulfate, zinc phosphate, and the like. Mixtures of divalent or polyvalent metal salts of oxyacids, such as aluminum sulfate and zinc phosphate, can be used in the process of the invention. Divalent or polyvalent metal salts of organic or inorganic oxyacids are sometimes referred to as "modifiers"
Say. These modified catalysts are believed to have a complex structure, possibly consisting of a mixture of species, some of which may even be catalytically inactive. Those species that are catalytically active have the formula = [R1-Xl-N-Yl
-[83-Y2]j-[1'f2-X2-R21g(i
) (wherein R and R2 are independently hydrogen or a residue of an organic compound having at least 61m active hydrogen, X and X2 are independently oxygen, sulfur or nitrogen, MM and M3 are independently divalent or polyvalent metals, with the condition that at least one of M1%M2 and M3 is calcium, and Y and Y
2 is independently a divalent or polyvalent oxyacid anion with a valence of 2 to 6, and at least one of Y□ and Y2 is a divalent or polyvalent oxyacid anion with a valence of 2 to 6; in some cases oxygen, sulfur, or nitrogen, j is an integer having a valence of 0 to about 100, and f and g are such that when j has a valence of O, the sum of f+g is the valence of Y□. and f and g are integers with a value such that if j has a value other than 0, then the sum of f+g is Y,
+ [M3-Y2.

0 formula (1
) is understood to be speculative only. As used herein, divalent means a valence of two and multivalent means a valence of more than two.

For purposes of the present invention, including the foregoing claims, formula (1) includes polyvalent 1<2> requirements for MM and M3, and such polyvalent requirements are defined by formula (i).
It is understood that it is adequately filled within.

The polyvalent requirement of M3 is R1-X 1- or R2X2-
It is also understood that it can be satisfied by

Another aspect of the invention provides that (i) a calcium metal or a calcium-containing compound, such as calcium oxide or calcium hydroxide, is at least partially reacted or solubilized by mixing with an activator so that the calcium has a titratable alkalinity. and (ii) reacting the calcium-containing composition with at least one divalent or polyvalent metal salt of an oxyacid under effective reaction conditions to produce an alkoxylation catalyst. As used herein, the term "solubilize" refers to a method for preparing a modified calcium-containing alkoxylation catalyst comprising: This means that solubilization appears to be occurring. However, this term is not intended to be limited to the production of truly dissolved calcium species, which may or may not be present.

Solubilization can be carried out by treating either calcium oxide or calcium hydroxide with the general formula Z -X-Q-Y-Z'b, where X and Y are selected from the group consisting of oxygen, nitrogen, sulfur and phosphorus. are the same or different electronegative (with respect to carbon) hetero (i.e., non-carbon) atoms, a and b are the same or different integers that satisfy the valence requirements of X and Y, and Q is is electropositive or essentially neutral with respect to X and/or Y, does not interfere with solubilization, and contains at least one carbon atom, preferably of the formula
and R5 are the same or the same and are selected from the group consisting of hydrogen and lower alkyl groups and alkylene groups having 1 to 4 carbon atoms, and P is an integer from 2 to 4). and Z and Z' are either the same or independently hydrogen or an organic group that does not interfere with the function of the activator for its intended purpose, i.e. its solubilizing and/or stabilizing action. It is carried out by mixing with an activator, and then the oxyacid is
The calcium-containing composition reacts with a valent or polyvalent metal salt to form a catalyst that is catalytically active in the alkoxylation of compounds having active hydrogen, especially alcohols.

Solubilization of calcium oxide or hydroxide results in the production of an alkaline slurry whose alkalinity can be detected and measured by titration, referred to herein as "titratable alkalinity."

Alkoxylates can be produced by directly contacting the modified calcium-containing catalyst composition with an alkylene oxide to form an alkoxylate of the activator itself when it has active hydrogen. If the activator does not have active hydrogen, it is preferred to remove excess activator before alkoxylation.

According to still other embodiments of this aspect of the invention, either before or after the reaction of the calcium-containing composition with the divalent or polyvalent metal salt of the oxyacid, under conditions in which an exchange reaction occurs. an exchange reaction with at least one organic compound having active hydrogen, such as an alcohol having a higher boiling point (and usually a longer carbon chain length) than the activator, to produce the corresponding catalytically active high-boiling derivative. This latter catalyst species can then be contacted directly with an alkylene oxide to produce the high boiling alkoxylate.

The alkoxylation process of the present invention comprises an alkylene oxide and at least one active hydrogen in the presence of a catalytically effective amount of a modified calcium-containing catalyst as described above.
It involves a condensation reaction with a species of organic compound. The modifier provides a normal equivalent weight to the anion of the metal that is sufficient to narrow the distribution of the alkoxylated product mixture and provide at least one alkoxylated species in an amount of at least about 20% by weight of the mixture. Approximately 0.2 to 0.9 times, for example 0.35 to 0.85 times the amount required for
Used at 0.75 times the amount. The modified calcium-containing catalyst is prepared under sufficient agitation to ensure a relatively uniform product. Preferred divalent or polyvalent metal salts of oxyacids are metal sulfates.

The modified calcium-containing catalyst has at least about 10
Preferably at least about 20, perhaps from 20 to 50,
Many are manufactured in media with dielectric constants of about 25 or 30-45.

According to the invention, alkoxylated product mixtures with a narrow but balanced distribution of alkoxylated species are obtained. These product mixtures do not contain relatively high amounts of fairly high-grade alkoxylated components, i.e., those with at least three more alkoxyl groups than the average peak alkoxylate species; advantageously, these narrow distributions are , can be obtained when the most alkoxylated component has four or more alkoxy units, ie in a region where conventional catalysts provide a relatively wide range of alkoxylated species.

The alkoxylated product mixture produced by the process of the invention is characterized by a molar ratio of reacted alkylene oxide per active hydrogen of at least about 4, and possibly from about 4 to 1.
6 or 24, preferably about 5 to 12, and an organic compound having at least one active hydrogen. These product mixtures will account for at least about 20%, perhaps about 20-30 or 40%, most often about 20-30% by weight of the composition.
The alkoxylation mixtures of the present invention having at least one alkoxylation component constituting 30% by weight also have a relatively symmetrical distribution.

Thus, the portion of the product mixture that has three or more oxyalkylene units (relative to active hydrogen sites on the organic compound) than the peak alkoxylated species is 1, e.g., often less than about 12% by weight of the mixture, perhaps 10
Less than 1% by weight, mostly about 1-10% by weight, which is relatively small.
Similarly, alkoxylated species with fewer oxyalkylene groups (relative to the active hydrogen sites of the organic compound) than 3 or more oxyalkylene groups from the average peak alkoxylated species will be less than 1, e.g., less than about 15% by weight of the mixture, perhaps about 1
Generally, alkoxylates with one more and one less oxyalkylene unit are the most abundant alkoxylated species, usually relatively small, less than 0% by weight, often about 0.5-10% by weight. 0.6 against
:1 to 1:1 by weight.

Preferred alkoxylated product mixtures of the present invention have the formula % Formula %) where n is the number of oxyalkylene groups to reactive hydrogen sites for one alkoxylated species of the composition (n must be at least equal to 61). ), h is the weight average oxyalkylene number, A is the weight percent of the predominant alkoxylated species in the mixture, and P is the weight percent of n in the mixture, within plus or minus 2%. % of alkoxylated species with oxyalkylene groups (relative to active hydrogen sites)]. This distribution relationship generally fits when n is between 5+4 and 5+4.

To this end, if the next higher and lower congeners are each present in a weight ratio of less than 0.9:1 to the most abundant alkoxylated species, then the average peak alkoxylated species is equal to the most abundant alkoxylated species. Defined as the number of oxyalkylene groups (relative to active hydrogen sites). If one of the adjacent congeners is present in a weight ratio greater than that amount, then the average peak alkoxylated species has an amount of oxyalkylene groups equal to the number average of the oxyalkylene groups of those two species. , is the weight average of the oxyalkylene groups of the alkoxylated species in the mixture (including unreacted alcohol). That is, h is equal to the sum of (n)(P,7) for all species present divided by 100.

Preferred alkoxylation product mixtures of the invention are poly(
oxyethylene) gelcols, i.e. “Carbo’7
9. CARBOWAX J (trademark) and fatty alcohol ethoxylates, including "TERGITOL J (trademark)"
``Bowax'' is a registered trademark of Union Carbide Company for a series of poly(oxyethylene) glycols. Ethylene glycol can be used to make carbowax-based poly(oxyethylene) glycols, and these carbowax-based poly(oxyethylene) glycols can also be used to produce higher molecular weight carbowax-based poly(oxyethylene) glycols. For example, carbowax-based poly(oxyethylene) glycol 200 can be used to produce carbowax-based poly(oxyethylene) glycol 400.
can be manufactured. Specifically, carbowax-based poly(oxyethylene) glycols are liquids,
Also, when W is greater than or equal to 4, the general formula H(O
CH2C)12) It is a solid polymer of wOH. in general,
Each carbowax-based poly(oxyethylene) glycol is associated with a number corresponding to its average molecular weight. in general,
The process of the present invention is not preferred because carbowax-based poly(oxyethylene) glycols having an average molecular weight of about 600-800 or more are used as starting materials.

Because such carbowax-based poly(oxyethylene) glycols are solid at room temperature (although they are liquid at reaction temperatures, e.g. 110°C), useful carbowax-based poly(oxyethylene) glycols )
Examples of glycols have an average W number of 4 and 190-200
carbowax-based poly(oxyethylene) glycol 200 having a molecular weight range of 1; carbowax-based poly(oxyethylene) glycol 400 having an average W number of 8.2 to 9.1 and a molecular weight range of 380 to 420; and 1
It is a carbowax-based poly(oxyethylene) glycol 600 having an average W number of 2.5-13.9 and a molecular weight range of 570-630.

"Targitol" is a series of ethoxylated nonylphenols, primary and secondary alcohols, i.e. nonionic surfactants and sodium salts of acidic sulfuric esters of secondary alcohols having 10 to 20 carbon atoms; That is, it is a registered trademark of Union Carbide Company for anionic surfactants. Examples of Tergitol-based nonionic surfactants include the general 2〇H(CH) CH(C8)-〇-(CH2CH20), H32x3 (wherein X has a value of 9 to 11 and y is about 1 There is a Tergitol S-based nonionic surfactant with a higher valence). Examples of Tergitol-based anionic surfactants include C4H9C1'l (C2H5)CH2SO4-H
a Tergitol anionic 08; C4H9C
H(C2H,,)C2H4CH-(804Ha)CH3
Tergitol anionidzuku 4 which is CN(CH3)2
: and CHCH(CH)CHCH-(304Ha)C2H4C
Tergitol anionic 7 which is H(C2H5)2
There is.

As mentioned above, the modified calcium-containing catalyst of the present invention is a divalent or polyvalent metal salt of an organic or inorganic oxyacid such as calcium sulfate, aluminum sulfate, zinc sulfate, zinc phosphate, etc. modified with a mixture of These modified catalysts are believed to have a complex structure, possibly consisting of a mixture of species, some of which may even be catalytically inactive. Those species that are catalytically active have the following formula: %Formula%]() where R and R2 are independently hydrogen or an organic residue of an organic compound having at least 61 active hydrogens; X and X2 are independently oxygen, sulfur or nitrogen; MM and M3 are independently divalent or polyvalent metals, with the proviso that at least one of M i , M2 and M3 is calcium; , Y and Y2
is independently a divalent or polyvalent oxyacid anion with a valence of 2 to 6, and at least one of Y□ and Y2 is a divalent or polyvalent oxyacid anion with a valence of 2 to 6 is oxygen, sulfur or nitrogen, j is an integer having a valence of 0 to about 100, and f and g are such that when j has a valence of 0, the sum of f+g is the valence of Y□. If they are integers with such valences, and f and g are valences other than 0, then the sum of f+g is y
It is understood that formula (i) which appears to have a structure of the type represented by + [M 3 Y 2 ] is an integer with a valency such that it is equal to the valency of j is speculative.

The alkoxylation product mixtures of the present invention are modified calcium-containing catalysts modified with divalent or polyvalent metal salts of strong oxyacids or mixtures thereof sufficient to provide a defined narrow distribution of alkoxylation products. given by using .

Alkoxylation conditions can be varied to others while still achieving a narrower distribution of alkoxylate products.

The catalytic modifier is at least one divalent or polyvalent metal salt of an oxyacid containing at least one, and most often at least about two, oxygen atoms, usually hydrated, doubly bonded to the nuclear atom. Contains.

Such divalent or polyvalent metal salts include, for example, the sulfates and phosphates of calcium, magnesium, zirconium, zinc and thorium. However, the use of sulfates generally provides the narrowest distribution.

Divalent and polyvalent anions of metal salts of oxyacids suitable for use in the present invention, such as Y and Y2, include, by way of example, sulfates, 800 batinates, such as VO, ri4-2'
Examples of metals that can be incorporated into the 24 modifier include beryllium, magnesium, calcium,
Strontium, barium, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper,
Zinc, cadmium, mercury, boron, aluminum, gallium, indium, thallium, carbon, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, sulfur, selenium, tellurium, cerium, praseodymium, neodymium, promethium, samarium, europium, Gadolinium 1, terbium, dysprosium, holmium, erbium, thulium, ibuterbium, lutetium, thorium, 10
There is actinium, uranium and plutonium.

Such metals can also be incorporated into modified calcium-containing catalyst structures by the method of the invention to obtain calcium-containing bimetallic or multimetallic catalysts in which the metals incorporated into the catalyst structure may be the same or different. 0 "2 metals" used in this specification may be the same or different 2
It means a metal, and [polymetal] means more than two metals, which may be the same or different.

Depending on the amount of modifier used and the method of introducing it to prepare the catalyst, a desired narrow distribution is achieved in which the at least one alkoxylated species is present in an amount of at least about 20% by weight of the composition. You can decide whether or not. Without wishing to be limited by theory, an active catalyst for producing a narrow distribution of alkoxylated products has the formula (1
) is considered to consist of calcium atoms and/or one or more metal atoms associated with the modifier anion such that the one or more metal atoms are activated. It will be done. The amount of modifier added will be about 0.2 to 0.9 times the amount needed to achieve normal metal equivalents for the anion, perhaps about 0.45 to 0.7.
There are 5 times the amount.

Generally, during reforming, the precursor composition to the calcium-containing catalyst has the following formula: %() where R1, R2, Xo, , X3 and X4
are independently oxygen, sulfur or nitrogen, and f' and g' are integers having a valence such that when j has a valence of 0, the sum of f' + g' is equal to the valence of X3. ,
And f' and g' are f' when j has a value other than 0.
+g” is X 3 + [M 4 X 4 ]
(is an integer with a valence equal to the valence of 3)
It can be expressed by R and R2 are independently double bonded oxygen (when the organic compound is a carboxylic acid),
Mana is a petro atom (such as oxygen, sulfur, nitrogen or phosphorus)
For example, when the organic compound is a glycol, a polyamine, an ether of a glycol, etc.). R and R
It is understood that formula (ii), where 2 is often from 1 to 20 carbons, is only speculative.

For the purposes of the present invention, including the foregoing claims, formula (ii) includes polyvalent requirements for M4, and such polyvalent requirements are suitably satisfied in formula (ii). is understood. It is also understood that the polyvalence requirement of M in [M4-X4] may be satisfied by RtXi- or R2X2-: The modifier produces the desired catalytically active modified calcium-containing species. It seems possible.

However, depending on the other conditions during the modification, the amount of modifier will provide the optimum catalyst with respect to selectivity and reaction rate during the alkoxylation step. Accordingly, one aspect of the present invention is to provide a sufficient level of modification to achieve a narrow distribution of the alkoxylated product mixture.

The medium containing the modified calcium-containing catalyst can also influence whether the resulting modified calcium-containing catalyst provides the desired narrow distribution of alkoxylation products produced. It can be observed that if the medium has a low dielectric constant substance as the main component, ie the solvent, the modifier forms a separate liquid phase and the difficulty to obtain a homogeneous mixture increases.

On the other hand, for solvents that are too polar, organic components associated with calcium or metal atoms may be replaced by the solvent.

Therefore, excess water is typically avoided during modification of calcium-containing catalysts. In most cases, the medium and the organic compound supplying the calcium or metal atoms are the same. Particularly convenient vehicles include ethylene glycol, propylene glycol, diethylene glycol, glycerin, butanediol, 1.3-70 pandiol, and the like. If it is not intended to be a reactant for the production of alkoxylates, it is convenient that the medium used has a sufficiently low boiling point so that it can be easily removed by distillation from the mixture of catalyst and organic compound reactant. It is. Most often, the medium will consist of a solvent having at least two heteroatoms, such as the active agents mentioned herein.

Preferably, the modifier is added while the calcium-containing precursor composition is being vigorously stirred. In this regard, it is preferred to slowly add the modifier to the calcium-containing catalyst; generally less than 10% of the modifier to be added is always added to the calcium-containing catalyst. The addition of the modifier is carried out at a convenient temperature, e.g. about 10-160°C, perhaps about 50-
It can be carried out at 150°C. Preferably, a nitrogen atmosphere is advantageous. It is advantageous to introduce the modifier in aqueous form.

Calcium-containing catalysts having substituents of the formula RX - and -X2R2 can be prepared by any suitable method. For example, calcium metal or calcium-containing compounds such as calcium hydride or calcium acetylate or calcium as described below. Catalyst precursors can be prepared by reacting other suitable sources of with organic compounds containing active hydrogen atoms of the formula RXH or HX2R2. With respect to compounds having high molecular weight, e.g. 4 or more carbons, lower molecular weight, more reactive and volatile compounds of formula RXH or HX2R2 (e.g. 1 to about 3 carbon atoms) It is generally preferred to use a compound containing a compound such as ethanol, ethylamine, ethylene glycol, etc.) and then replace the substituent with a higher molecular weight substituent while removing the lower molecular weight material by volatilization. Alternatively, a calcium-containing catalyst can be prepared from quicklime or slaked lime by the method described below. This catalyst precursor is then reacted with a divalent or polyvalent metal salt of an oxyacid to form a modified calcium-containing catalyst. Produce an alkoxylation catalyst.

Compounds having the formulas RXH and HX2R2 include those organic compounds having active hydrogens as described in connection with the alkoxylation products of the present invention, such as alcohols, phenols, carboxylic acids and amines. Often, compounds with formulas RXH and HX 2 R2 are alcohols. When performing exchange reactions to impart high molecular weight substituents to calcium atoms or other metal atoms, it is possible to improve the modification process by performing a modification before exchange and using a low molecular weight material as the exchange substituent. Organic compounds having active hydrogen suitable for use in the present invention include products of hydroformylation/hydrogenation reactions.

Examples of calcium-containing compounds/compositions for use in the present invention include soluble calcium-containing compounds/compositions themselves or reactants in the alkoxylation process, such as calcium that can be converted to a soluble form upon interaction with an activator. There are compounds/compositions included. Examples of specific calcium-containing compounds/compositions include one or more reaction products of calcium with various alcohols (alcolades such as calcium alkoxides and phenoxides) as well as oxides, hydroxides, Ammonides, amides, thiolates, carbides, thiophenoxides, nitrides, thiocyanates and carboxylate compounds such as acetates, formates, oxalates, citrates, benzoates, laurates and stearates. Preferred calcium-containing compounds are calcium oxide and calcium hydroxide or mixtures thereof;
And preferred calcium-containing compositions are calcium alcoholades.

The preparation of modified calcium-containing catalysts from calcium metal or calcium-containing compounds such as calcium hydride or calcium acetylate or other suitable calcium sources described above is typically carried out at elevated temperatures, e.g.
The organic compound undergoing the substitution, carried out at 0° C. or above and in a liquid medium, is usually provided in excess of the amount required for the reaction with the calcium-containing reactant. Therefore, the weight ratio of calcium-containing reactants to organic compounds is often about 0.
Of: Within the range of 100 to 25:100. If desired, the reaction can be carried out in the presence of an inert liquid solvent. The exchange reaction is also carried out at high temperature and, if necessary, under reduced pressure to facilitate the removal of volatile components; the temperature is approximately 50°C.
~250°C, probably around 80-200°C or 250°C
C. and the pressure (absolute) is often in the range 1 mbar to 5 bar, such as about 10 mbar to 5 bar.

It is generally desirable that the organic substituents of the modified calcium-containing catalyst composition represent the "initiator" component of the alkoxylation process; the WR initiator component is an organic compound having at least one active hydrogen with which the alkylene oxide reacts. It is.

The alkoxylation is carried out using a catalytically effective amount of calcium-containing catalyst, for example from about 0.001 to 10% by weight, often from about 0.5 to 5% by weight, based on the weight of the initiator component. The catalysts substantially retain their activity during the alkoxylation, regardless of the amount of alkylene oxide used. Therefore, the amount of catalyst is based on the amount of initiator fed to the alkoxylation zone rather than the extent of alkoxylation being performed.

Typically, the calcium-containing catalyst and initiator components are mixed, then the alkylene oxide is added at reaction temperature until the desired amount of alkylene oxide has been added, the product is then neutralized, and the product mixture is optionally added. The product can be completed by any procedure involving stripping, passing or further reacting of unreacted initiator material from.

The temperature of alkoxylation is sufficient to provide adequate reaction rates without deterioration of the reactants or reaction products.

The temperature is often between about 50°C and 270°C, for example about 10°C.
It is in the range of 0°C to 200°C. Although the pressure can also vary widely, it is preferred to use pressurized reactors when using low boiling alkylene oxides such as ethylene oxide and propylene oxide.

It is preferred to agitate the alkoxylation reaction medium to ensure good dispersion of the reactants and catalyst throughout the reactants, and the alkylene oxide is typically mixed at a rate close to that at which it can be reacted. Added.

Neutralization can facilitate recovery of the catalyst from the alkoxylation product mixture.

When neutralizing, acids should be avoided that may tend to form catalyst-containing gel structures, ie solids that clog the filter equipment. Conveniently, sulfuric acid, phosphoric acid, 10-pionic acid, benzoic acid, etc. are used.

The present invention provides a preferred procedure whereby calcium oxide (quicklime) and its hydrate, calcium hydroxide (slaked lime) (both referred to herein as "lime"), are effectively used to produce alcohol, Catalytic species can be prepared which are active in the alkoxylation of organic compounds having at least one active hydrogen, such as in particular long chain fatty alcohols, carboxylic acids, amines, polyols and phenols. This is achieved by the following general method.

The catalytic agent is catalyzed by contacting the lime with the activator under conditions such that the lime and the activator react or interact to form one or more catalytically active derivatives (hereinafter collectively referred to as "precursors"). Produce precursor materials. The active agent can be a compound having the formula % where each term is as defined above. Calcium-containing alkoxylation catalysts incorporating precursors of this reaction are suitable for the alkoxylation of alcohols, especially primary alcohols such as long-chain fatty alcohols, or mixtures thereof, used as initiators in the production of nonionic surfactants. It is particularly effective for However, calcium-containing alkoxylation catalysts that incorporate precursors can also be effectively used in the catalysis of various organic compounds with active hydrogen. For example, if the activator is ethylene glycol, the precursors can be It can be readily utilized to catalyze the alkoxylation of ethylene glycol to produce ethylene glycol-initiated poly(oxyalkylene) glycols having desired nominal molecular weights and relatively narrow molecular weight distributions. As yet another example, if the activator is the monoethyl ether of ethylene glycol (MEBG) and the precursor is directly alkoxylated with ethylene glycol, the product will have a composition whose composition depends on the molar ratio of ethylene glycol to MEEG. It is a mixture of ethoxylates of MEBG.

As used herein, the term "excess active agent" refers to the amount of active agent that does not bind chemically or physically to calcium and therefore can be removed by simple physical means. The technique used for this operation is not limited; vacuum stripping is preferred due to its simplicity and efficiency, but evaporation and other known methods can also be used.

The precursor is obtained as a finely divided solid in a slurry that can be easily separated from the reaction mixture by filtration, decanethisilane or similar methods. The products so obtained, whether modified with divalent or polyvalent metal salts of oxyacids or not, are catalytically active in alkoxylation reactions.

A particularly desirable feature of the present invention is that the catalyst can be used to specifically obtain alkoxylate surfactants with narrow molecular weight distributions, low pour points, and low amounts of unreacted initiator components. .

In this use, the catalyst is brought into contact with an initiator component, such as an alcohol, under conditions in which the reaction occurs to effect an alcohol exchange (also referred to as alkoxide exchange) reaction. Thus, it exists as an alcoholade of calcium, which is the active species of the initiator alcoholoxylation reaction. This reaction mixture is then reacted with one or more alkylene oxides, such as ethylene oxide, according to known methods,
Produce the desired surfactant.

Referring now to the structural formulas described above for the activator, X and Y are preferably separated from each other by one or more carbons;
For example, in the beta position to each other and preferably oxygen, as in ethylene glycol, or oxygen and nitrogen, as in monoethanolamine.
However, X and Y may also be sulfur or phosphorus. Examples of other useful compounds are ethylenediamine, tomethylethanolamine, tetrahydrofurfuryl alcohol, 2-mercaptoethanol, 1,2-propylene glycol, 2-methylthioethanol, 2-ethoxyethanol, diethylene glycol, 1,3-propanediol. and 1,4-butanediol.

2 and 2' are the same or the same radicals, optionally substituted, and at least one of 2 and 2' is often hydrogen, lower direct or branched alkyl having 1 to 4 carbon atoms, 2 selected from the group consisting of alkylene having ~6 carbon atoms, phenyl or lower alkyl substituted phenyl, cycloalkyl having 3 to about 6 carbon atoms, and alkylene or heteroatom substituted alkylene rings.

In the activator, Q can consist of a carbon chain of up to 6 carbons between X and Y. However, 2- to 4-carbon chains are preferred. This is because the activation power of X and Y is maximized at such chain lengths. Of these,
A 2-carbon chain length is particularly preferred. Very favorable implementation! 9
, Q is the 2-carbon chain length, and its structural formula is as follows.

(wherein Z, Z', X, Y, a and b are as defined above and R6, R7, R8 and R9 are preferably hydrogen, but optionally substituted 1 It may be a lower alkyl or alkylene group having up to 4 carbon atoms, or it may be any other group that does not interfere with the effectiveness of the active agent for its intended purpose.

Q may also be an optionally substituted cyclic, preferably cycloalkyl having up to 6 carbons, as can be represented by the formula: Compounds falling within this description include 4
-methoxycyclohexane, 1,2-diol, 2-aminocyclopentanol and 2-methoxycyclopentanol.

Similarly, either X or Y, or both, together with the carbon atom adjacent to either of them, can be part of a ring structure as represented by the formula: Certain compounds exhibiting such structures include tetrahydrofurfuryl alcohol, furfuryl alcohol, 2-hydroxyethylaziridine, 1-(N-methyl-2-pyrrolidinyl)ethanol, and 2-aminomethylpyrrolidine.

Furthermore, X and Y are themselves of the formula: can be part of the same ring structure containing Q according to

Examples of such compounds are piperazine, 4-hydroxymethyl-2,2-dimethyl-1,3-dioxolane, 2.
6-dimethylmorpholine and cyclohexanone ethylene ketal.

Many other ring structures, whether saturated or unsaturated, substituted or unsubstituted, are likewise possible and are within the scope of this invention.

A limitation observed in Q and the overall structure of the above formula is that the activator must be able to at least partially solubilize CaO and/or Ca(oH)2, which is normally insoluble. CaO and Ca(OH)
Solubilization of 2 is believed to be the threshold step that makes these previously inaccessible materials available.

Without wishing to be bound by any particular theory, this solubilization is achieved by the electron-withdrawing effect of the heteroatoms X and Y on adjacent carbon atoms, thereby increasing the acidity of the active agent molecule, which also appears to help participate in the formation of complexes with calcium, as exemplified by Thus, provided that it does not eliminate or neutralize the electronegativity of the heteroatoms and thus does not prevent the activator from performing its intended purpose of at least partially solubilizing CaO and/or ca(OH)Z. The structure represented by the formula % is satisfactory. It is believed that this may provide a stabilizing effect, such as thermal stability at high temperatures, thereby allowing the production of the desired final catalytically active species.

As the lime is solubilized, the alkalinity of the medium increases. Therefore, increased alkalinity can be used as a screening technique to see if it is useful as an activator. In this test, the CaO
Determine the alkalinity of approximately 1 g or more calculated as However, it should be noted that this test cannot be used reliably for active drug candidates containing amines, as amines interfere with this test.

As mentioned above, in the solubilization step of the method of the present invention, Ca
O and/or ca(OH)2 are mixed with the activator to form one or more precursor species. The purpose of this processing is
It is necessary to solubilize enough lime to be catalytically effective in the alkoxylation reaction. Thus, the concentration of lime can be either below or above its maximum solubility in the activator, provided that enough lime is solubilized to be catalytically effective. However, as a general guideline,
The concentration of lime used in the first step should specifically be in the range of about 1-2% relative to the activator, although the lime should normally be present somewhat more than its solubility in the activator. ,
Lime concentrations above about 30% are rarely considered desirable.

The temperature for this method is considered non-limiting and is about 5
Range from 0°C to the boiling point of the activator, typically 200°C
Temperatures can completely exceed .

It is desirable to operate in the range of about 90-150°C, preferably about 125-150°C, and the system is either under vacuum or pressure to maintain the desired temperature while retaining the active agent in the liquid phase. be able to. Advantageously, the temperature and pressure conditions are such that water can be 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 this step of the method, lime is simply added to the activator in a stirred reaction vessel under sufficient agitation to form a slurry of lime for a sufficient period of time to solubilize at least a portion of the lime. generate. This step is usually accomplished in about 1 to 4 hours. The amount of lime solubilized will of course depend on the concentration of lime present, the potency of the activator used and the temperature, time and agitation used. Ideally, the desired amount of lime is solubilized for the subsequent alkoxylation reaction. Lime sources for this step include commercially available quicklime or slaked lime. This is because the impurities typically contained in such lime do not appear to have a significant adverse effect on the catalyst formed by the process of the present invention.

The resulting lime/activator precursor is then reacted with at least one divalent or polyvalent metal salt of an oxyacid to produce a catalyst for an alkoxylation reaction and to narrow the range of alkoxylation products. improve. This is the case, for example, when ethylene oxide is added to a substance used as an activator, such as ethylene glycol, to produce poly(oxyethylene) glycols of the desired molecular weight.

When the catalyst is used to produce surfactants or other alkoxylation products using initiators, the exchange can be made as described above.

For example, in the manufacture of surfactants, the catalyst of formula (i) above is added to a stirred reaction vessel containing a surfactant range alcohol or mixture of such alcohols, typically a 01□ to C14 alcohol. can do.

The concentration of precursor used can vary widely, but ideally is approximately the concentration desired for the subsequent alkoxylation reaction.

The temperature during the exchange reaction can be any temperature at which the reaction occurs, but ranges from about 100 to 250°C, and the pressure can be adjusted to achieve these temperatures. If the exchange is carried out, the activators selected are those in which the majority of
Approximately 2
It should have a boiling point below 00°C. The resulting alcohol exchange product is suitable for direct use as a catalyst in an alkoxylation reaction for producing surfactants starting from one or more exchange alcohols.

Catalysts prepared by the method described above are finely divided (e.g. about 5
It is often a stable slurry of micron) particles, is strongly basic (pH: about 11-12), and contains an excess of unmodified calcium-containing species.

The catalyst precursor of formula (ii) above, including its alcohol exchange product, is modified with a divalent or polyvalent metal salt of an oxyacid prior to its use as a catalyst for alkoxylation to obtain a narrow distribution of alkoxylate products. ask a question Mixtures of divalent or polyvalent metal salts of oxyacids can be used in the process of the invention. The modifier can be added at any time during catalyst preparation, but is generally added before the addition of the detergent range alcohol. The modifier can then be added as a solid or dissolved in a suitable solvent.

Although the exact chemistry of this procedure is not completely understood, this modification provides a demonstrable improvement to the overall process in that the molecular weight distribution is narrowed. Additionally, modified catalysts require little or no induction period for the alkoxylation reaction and also tend to have increased reaction rates over their unmodified analogs. In contrast, addition of divalent or polyvalent metal salts of oxyacids to conventional catalysts, such as potassium hydroxide, slows the rate of alkoxylation without having any beneficial effect on product distribution.

Advantageous results can be obtained if the catalyst is used in its "crude" state, ie without separation or purification from its reaction mixture. Nevertheless, if desired, the reforming facility can separate the catalyst from its reaction mixture, purify it, dry it, and store it. As such, excess activator or other organic material containing active hydrogen is removed by stripping, the resulting slurry is passed through, and the undried solids are reslurried in a solvent (e.g., tetrahydrofuran). filtered and refiltered,
And it can be achieved by a simple method, preferably by drying under reduced pressure. Although the solids thus obtained are catalytically active, they are often substantially less active than the catalyst in its "crude" state. However, despite the slow reaction rate, the desired narrow molecular weight distribution and other advantages can still be obtained.

It is a highly desirable and entirely unexpected advantage of this aspect of the invention that the entire process illustrated in the various procedures above for producing catalyst from lime is very amenable to process variations. .

Therefore, there is considerable flexibility in adding modifiers and how much modifier to use within reasonable limits. Similarly, unreacted activator can be removed in whole or in part before the exchange reaction, e.g. if used,
Alternatively, it may be left present during the exchange reaction; furthermore, the catalyst may be reused indefinitely, used and stored in its "crude" state, or some of the reaction rate may be increased by increasing the temperature. It can be purified and dried with loss.

The steps involved in carrying out the method of the invention are illustrated by the following description of the production of nonionic surfactants.

Means for carrying out the method of the invention are defined as "pea"
ked) J (narrow molecular weight distribution) can be illustrated by the following general method for producing a calcium-based alkoxylation catalyst slurry intended for use in the production of linear alcohol ethoxylates (nonionic surfactants).

As applied to the special case of the production of nonionic surfactants, the process of the invention is characterized by a fairly free operating range. This is particularly true in the preferred embodiment method of producing modified catalysts. From the point of view of the chemical action that occurs, the preferred production of modified calcium-containing catalysts is
There are two separate processes. Steps 1 and 2 consist of the following reactions: Step 1 - Reaction of lime (or a mixture of large amounts of lime and small amounts of other alkaline earth bases) with a suitable activator to produce a catalyst precursor. .

Step 2 - Reaction of catalyst precursor with detergent range alcohol to effect exchange of organic groups derived from the activator for organic groups derived from the detergent range alcohol.

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 detergent range alcohol slurry.

In the production of unmodified calcium catalyst as an intermediate,
Steps 1 and 2 above can be combined into one operation in which the lime is reacted with a mixture of an activator and a detergent range alcohol. When using useful activators (e.g., ethylene glycol, 1,2-propylene glycol, ethylene glycol monoethyl ether, etc.), the activity tends to minimize color build-up in the catalyst slurry. This alternative procedure of combining the agent with a detergent range alcohol is often preferred. From the point of view of the properties of the final product, these two layers are equally acceptable.

Modification methods in which the activator is provided in a slurry of a detergent range alcohol and a calcium base, or a detergent range alcohol is provided in an activator slurry (or solution in some cases) of a calcium base, are also operationally It is doable.

However, their adoption does not provide any discernible advantages over batch charging formats.

The process for producing the reforming catalyst includes a third main processing operation that is a separate step in terms of the chemistry that occurs, similar to the operations of steps 1 and 2.

Step 3 - Treatment of unmodified catalyst slurry in detergent range alcohol with at least one divalent or polyvalent metal salt of an oxyacid.

This process provides a highly active modified calcium-containing catalyst in the form of a detergent-grade alcohol slurry. Prior to use in the ethoxylation reaction to produce nonionic surfactants, the product slurry is typically subjected to a vacuum drying process. The modifier charge is determined by the initial lime charge, and more preferably by adjusting the alkalinity of the lime/activator reaction mixture sample using CO, OIN Furcol MCI, possibly in the presence of a bromothymol blue indicator.
can be based on any of the "active catalyst" values obtained by titrating the active catalyst content). A particularly convenient method is to perform a titration in the middle of the lime/activator reaction.
The amount of the modifier to be charged is determined by the alkalinity value obtained when a certain level of alkalinity is reached. A particularly convenient and effective method is to add the modifier in an amount of about 50% of this "constant" alkalinity value, monitor the lime/activator reaction by zero titration and based on this analysis. Determining the modifier charge using the amine is often the preferred method, but cannot be used for amino-functional activators because the amine functionality interferes with the alkalinity analysis. It is from. In such cases, the preferred method is to base the modifier charge on the alkalinity value obtained by titrating a detergent range alcohol slurry free of catalyst activator (stripped). It is.

Since the method affords such a wide range of freedom of operation, there is no single method that can be said to represent the general method; this consideration nevertheless suffices to describe the method. The steps are as follows:

Lime (commercially available calcined at 600℃ for 6 hours)
and 2-ethoxyethanol (obtained from Union Carbide) into an appropriately sized stirred reaction vessel equipped with a reflux condenser, thermocouple, 10-stage distillation column, and nitrogen gas purge inlet. The weight ratio ranges from 60 to 80 parts per part. During the entire reaction period, only about 10~
The charge is brought to reflux temperature (approximately 135°C) with the refluxing solvent being removed overhead either continuously or intermittently at a rate sufficiently slow that only 15% of the initially charged solvent is removed overhead.
Heat under nitrogen purge for periods of 2 to 6 hours.

The purpose of this operation is to remove water from the system, either introduced with the reactants or produced by the chemical reaction. During the reflux period, the reaction mixture is periodically sampled to monitor the increase in "alkalinity" indicating the production of catalytically active material. The analytical method used for this purpose is titration with 0.0 IN HCr in 2-ethoxyethanol using a bromothymol blue indicator. The lime/activator reaction is considered complete if similar 'alkalinity J levels are obtained in two consecutive titrations. The normal time limit for reaching this point is about 4 hours.

At this point, when the reaction mixture is diluted with detergent range alcohol and ethoxylated, the amount of alcohol added is typically around 100 g per lime (>Ig calculated as CaO) used in the first reaction. The resulting mixture is cooled to about 75° C. and treated with sufficient modifier, preferably metal sulfate, under stirring to reduce about 60% (on an equivalent basis) of the lime/activator reaction mixture. Modify.

The temperature is then increased to remove the activator from the reaction mixture by distillation. When the kettle temperature reaches about 215-225°C and both the kettle product and the distillate are free of activator as indicated by gas chromatographic analysis (GC) (e.g. less than 1000 ppm by weight, often i.
Distillation continues until ooutppm (end of ppm).

The catalyst activator-free detergent range alcohol slurry thus obtained can be used directly as a charge to the ethoxylation reactor or, if desired, can be used to obtain the desired catalyst concentration in the slurry. It can also be diluted with enough dry detergent range alcohol. The final alkalinity j value of this slurry can optionally be obtained by the same titration method as described above.

The above method represents only one example of the many equally possible variations of the method of the invention. The following examples illustrate the use of other variants that are possible by various combinations of any of the available steps for the various operating steps.

The catalytic alkoxylation reaction of the present invention can be carried out, for example, by (1) batch operation, (2) continuous a! It can be carried out by conventional methods such as fixed bed operation and (3) continuous flow reactor operation. In batch reactors, the catalyst is kept suspended in the reactants by shaking or stirring. In a flow reactor, the catalyst is initially at a certain level.6 As the velocity of the reactant stream increases, the catalyst bed expands up to a second level, and at a critical velocity, the catalyst begins to flow violently turbulently. Fluid reactors are particularly effective in removing or supplying the heat necessary to maintain a constant catalyst temperature. Fluid reactors can only be used on a rather large scale since good fluidization requires a reactor larger than about 1.5 inches (about 3.8 cn) in diameter.

The method of the invention involves the use of calcium-containing catalysts for the alkoxylation of active hydrogen compounds, preferably hydroxyl-containing compounds such as primary or secondary alcohols, diols or triols. Mixtures of active hydrogen compounds can be used.

The alkoxylated product mixture produced by the process of the invention has the formula % [wherein R10 is an organic residue of an organic compound having at least one active hydrogen and S is comprised by the organic compound from at least 61]. is an integer up to the number of active hydrogens in which r consists of an alkoxylated species which can be represented by at least 0, and possibly an integer from 1 to about 50.

Organic compounds with active hydrogen include alcohol ff (1
hydric, dihydric and polyhydric alcohols), phenol, carboxylic acid! (monobasic, dibasic and polybasic acids) and amines (primary and secondary).

Organic compounds often contain from 1 carbon to about 100 to 150 carbons (for polyol polymers) and can have aliphatic and/or aromatic structures. Usually, the organic compound is selected from the group of monohydric, dihydric and trihydric alcohols having from 1 to about 30 carbon atoms. Organic compounds with active hydrogen can be products of hydroformylation/hydrogenation reactions.

Particularly preferred alcohols include methanol, ethanol,
10 panol, pentanol, hexanol, hexanol, octatool, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol, in-10 alcohol, 2-ethylhexanol, 5ec -butanol, isobutanol, 2-
Primary and secondary monohydric alcohols, which are straight chain or branched, such as pentanol, 3-pentanol and isodecanol. Particularly suitable alcohols are C3-C2
o Straight-chain and branched-chain primary alcohols (including mixtures), such as those produced by the "oxo" reaction of olefins.
, alcohols may be cycloaliphatic alcohols such as cyclopentanol, cyclohexanol, cyclohebutanol, cyclooctatool and aromatic substituted aliphatic alcohols such as benzyl alcohol, phenylethyl alcohol and phenylpropyl alcohol. good. Other aliphatic structures include 2-methoxyethanol.

Phenols include alkylphenols having up to 30 carbons such as p-methylphenol, P-ethylphenol, P-butylphenol, p-hebutylphenol, p-nonylphenol, dinonylphenol and P-decylphenol. Aromatic groups may also contain substituents such as halogen atoms.

2 or more hydroxyl groups, such as 2 to 6 hydroxyl groups and 2 to 3 hydroxyl groups
Alcohols (polyols) having 0 carbons include ethylene glycol, propylene glycol, butylene glycol, pentylene gelylcol, hexylene glycol, neobentylene gelylcol, decylene gelylcol,
There are diethylene glycol, triethylene glycol and diethylene glycol. Other polyols include 1°3-propanediol, pentaerythritol, galactitol, sorbitol, mannitol, erythritol, trimethylolethane and trimethylolethane.

Alkylene oxides that provide oxyalkylene units in the ethoxylated product include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2- and 2,3-bentylene oxide, cyclohexylene oxide, ■, 2-hexylene oxide, l.

Alkylene oxides such as 2-octylene oxide and 1,2-butylene oxide; Epoxidized fatty alcohols such as epoxidized soybean fatty alcohol and epoxidized soybean fatty alcohol; Aromatics such as styrene oxide and 2-methylstyrene oxide and hydroxy- and halogen-substituted alkylene oxides such as glycidol, epichlorohydrin, and ebibromohydrin. Preferred alkylene oxides are ethylene oxide and propylene oxide.

The choice of organic residue and oxyalkylene moiety will depend on the particular use of the resulting alkoxylated product. Advantageously, narrow distributions can be obtained using various compounds with active hydrogen, especially monohydric alcohols which provide the desired surfactants. Because of the narrow distribution of alkoxylation product mixtures, particularly attractive alkoxylation products are surfactants that seek a certain balance between hydrophilicity and lipophilicity. Therefore, the organic compound is about 8
It consists of monohydric alcohols having ~20 carbons, and the alkylene oxide often consists of ethylene oxide.

Although the method described here can selectively obtain narrow distributions of alkoxylates in which the most abundant species have as little as 1 mole of oxyalkylene per mole of active hydrogen sites, special advantages are that e.g. It is possible to provide a narrow distribution with high levels of alkoxylation with at least 4 oxyalkylene units. For some surfactant applications, the most common alkoxylated species have 6,7,8,9,10, II or 12 oxyalkylene units for the active hydrogen site.

For many surfactant applications, relatively few species have been found to provide the desired activity, ie, a range of plus or minus two 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 obtainable by the present invention improves the balance while providing mixtures exhibiting desirable physical properties such as cloud point, freezing point, viscosity, pour point, etc. For many of the alkoxylated mixtures of the invention, species within the range of 5±2 will account for at least about 75% by weight of the composition, and perhaps about 80-9% by weight of the composition.
Importantly, no single alkoxylated product is present in an amount greater than 50% by weight of the composition, and often the most abundant species It may be present in an amount of up to about 30% by weight, such as about 22-28% by weight, to provide a composition that improves the balance of the composition.

Another group of alkoxylated products are poly(oxyethylene) glycols. For example, tri-J-1/glycol and tetraethyl-1/glycol have uses in gas dehydration, solvent extraction, and the production of other products and compositions. These glycols can be produced by 1-xylation of ethylene glycol and diethylene glycol.

An advantageous method of the invention comprises a polyoxylate product composition comprising at least about 80, and perhaps about 80 = 95% by weight of I-diethylene glycol and tetra-diethylene glycol.

Among the most commercially important alkoxylation products are
Some use water or alcohols (monols, glycols, polyols, etc.) as initiators and ethylene oxide, propylene oxide or ethylene oxide/propylene oxide mixtures as l,2-alkylene oxide monomers. Such alcohol ethoxylates are widely used in applications ranging from heavy industrial applications such as solvents and palm oil to pharmaceuticals,
The calcium-containing catalysts of the present invention are suitable for a wide range of alkoxylation processes, encompassing an unbeatable structure, composition, and molecular weight for a variety of applications ranging from ectopy to the most sophisticated consumer applications such as in household products. Although the product is highly effective, gamma-lucoxylate 1 is intended to be used in elaborate consumer applications with strict product quality requirements.
This is particularly useful for m-phrases. Of the many types of alkoxylates used in such applications, two of the most prominent are poly(oxyethylene) glycols and fatty alcohol 1-gysylates. Carbowax, polyglycol (POLYGEYCOof-E) (
Trademark), PLuRACOl, ) (
Poly(oxyethylene) glycols, known by trade names such as ethylene glycol (trademark), are prepared by the ethoxylation of ethylene glycol or one of its congeners and have molecular weights ranging from about 200 to about 8,000. Manufactured throughout. Fatty alcohol oxylates, known by trade names of nonionic surfactants such as NEODOL(TM), ALFONIC(TM), Tergitol, etc., are linear or branched. Produced by ethoxylation of chain C10-C,6afKJ alcohols. They are produced with a range of about 300 to about 800 molecules IN. The calcium-containing catalyst of the present invention is a common homogeneous ethoxylation catalyst (NaOH1K,
It is in the production of these and other implementations of rare quality, xl-xylene l-, that they offer the greatest advantage over xl-xylene (OH, etc.).

The method of the present invention offers many advantages besides selectively providing a narrow distribution of alkoxyl notes. Provides safety benefits including: The use of divalent or polyvalent metal salts of oxyacids as modifiers also has operational advantages, such as minimizing corrosion of reaction equipment and equipment (removal of alkoxylation catalyst from the final product). give.

Hereinafter, the present invention will be further explained by examples.

Calcium-containing catalyst modified using common methods?
The amounts listed in Table A for ethylene glycol were added to a 7 tff, 7 reaction vessel equipped with a reflux condenser, thermocouple, mechanical stirrer and nitrogen purge inlet. The resulting mixture was heated to reflux (approximately 105 °C) under reduced pressure (15+nvz) and a constant nitrogen purge for a period of 4-5 h.
,. During this time, a total of about 452 distillates were removed overhead and analyzed for moisture lf: after a 7" C9 heating period, the mixture was cooled to a temperature of 60°C and Described in 1
~ metal sulfate then A-lfod (trade name) 121
4. Mixture of linear aliphatic alcohols from CI2 to Ct4 (approximately 55/453i Jit:ratio) [USA,
Vista, Texas
[commercially available from Chemica, d Colnp&n, y'] was added to the reaction mixture in Table AK specified in 'frOLi. This mixture was then heated to remove the ethylene chloride (and residual water) from the top of the column (I8
When the pot temperature reached 220°C (the top temperature was 208°C), the heating was removed and the contents were allowed to cool to outside air temperature. The resulting slurry was then transferred to a glass bottle under a nitrogen blanket (7) and kept capped until use. The amounts of each catalyst in this form were used to prepare the nonionic surfactant batch formulations described in Examples 8-14 below.
.

Table A 310 s,o Th(So,)23
10 5.0 Mg 5 (I44゜31
0 5.0 ZnSO43105, O
ZnSO4 3105, OZnSO4 3105, OCa50°310 5.0 LizSO431
05,0KE (So.

5.36 12.83 6.42 8!55 12 U5 5.71 6.05 Nominal So, : ZrO, United States as Zyl'jnium basic sulfate (ZBS) with molar ratio 0.6:1, Commercially available from Magnesium Electron, Inc., Flemington, Chassis.

Examples 8-14 and Comparative Examples C and D Nonionic surfactants were prepared using the general method. The reactor used for these productions was a 2-gallon stirred autoclave equipped with an automatic ethylene oxide supply system. In this system, the supply of diethylene oxide was controlled by a motor pulp to maintain a pressure of approximately 60 psig, and the 2-gallon stirred autoclave was supplied with the diethylene oxide as described in Table B.
fol'1214, ethylene oxide, and catalyst slurry (number of moles of raw material calcium, excluding optional metals in the filtrate modifier) were added in the amounts listed in Table B. The reaction was carried out under a nitrogen atmosphere (20 psig) at 140
The temperature is ℃. The ethylene oxide feed time and maximum reaction rate are also shown in Table B. The molecular weight distribution of the nonionic surfactant product was determined by gas chromatographic analysis (area%)
The results are shown in Table B.

The results from Table B illustrate the effectiveness of calcium-containing catalysts of the present invention modified with divalent or polyvalent metal salts of oxyacids. Examples 8 to 14 illustrate two aspects: a narrow distribution of alkoxylated species (5 species) and at least one alkoxylated species comprising at least about 20% of the product mixture; Preparing a nonionic surfactant with i, -'7'':,.

Although the present invention has been explained in detail above and in Example 2,
It should be understood that it is limited by stiffness.
However, the present invention covers the general idea. Aspiration note 1. ) Modifications and embodiments may depart from the spirit and scope of the invention.

Claims (1)

[Claims] 1. (a) A calcium metal or a calcium-containing compound having the formula Z_a-X-Q-Y-Z'_b (wherein X and Y are from the group consisting of oxygen, nitrogen, sulfur and phosphorus) are the same or different electronegative heteroatoms selected, a and b are the same or different integers satisfying the valence requirements of X and Y, and Q is the corresponding electrically negative heteroatom of X and/or Y. or essentially neutral, and Z and Z' are the same or different and are either hydrogen or an organic group that does not interfere with the reaction or solubilization). (b) reacting or solubilizing the calcium-containing composition at least partially by reacting or solubilizing the calcium-containing composition with a titratable alkalinity; A method for producing an alkoxylation catalyst comprising reacting it with at least one divalent or polyvalent metal salt. 2. The calcium-containing compounds are oxides, hydroxides, carboxylates, alcoholates, ammonides, amides, nitrides, thiocyanates, thiolates, carbides, thiophenoxes, and substances that are converted in situ to the aforementioned compounds in the method. 2. The method of claim 1, wherein the method is selected from: 3. The method of claim 1, wherein said calcium-containing compound is a carboxylate selected from acetates, formates, oxalates, citrates, benzoates, laurates, stearates and substances which are converted in situ to said compounds in said process. . 4. The method according to claim 1, wherein the calcium-containing compound is calcium oxide, calcium hydroxide, or a warm mixture thereof. 5. The method of claim 1, wherein the calcium-containing compound is a calcium-containing alcoholade. 6. The activator has the formula ▲ Numerical formula, chemical formula, table, etc. 2. The method of claim 1. 7. The method of claim 1, wherein said activator is ethylene glycol. 8. The method of claim 1, wherein said activator is 2-ethoxyethanol. 9. The method according to claim 1, wherein the divalent or polyvalent metal salt of the oxyacid is a metal sulfate. 10. The method according to claim 1, wherein the divalent or polyvalent metal salt of the oxyacid is a metal phosphate. 11. The method according to claim 1, wherein the divalent or polyvalent metal salt of the oxyacid is a mixture of a metal sulfate and a metal phosphate. 12. The method according to claim 1, wherein the divalent or polyvalent metal salt of the oxyacid is zirconium sulfate. 13. The method according to claim 1, wherein the divalent or polyvalent metal salt of the oxyacid is zinc sulfate. 14. The method of claim 1, comprising the additional step of reacting the alkoxylation catalyst with the alcohol under conditions in which an alcohol exchange reaction occurs with the alkoxylation catalyst, thereby producing the corresponding alcohol derivative. 15. The method according to claim 14, wherein the alcohol is n-dodecanol. 16. The method of claim 14, wherein the alcohol is a mixture of C_1_2 to C_4_4 alcohols. 17. The method of claim 14, wherein the alcohol is a product of a hydroformylation/hydrogenation reaction. 18. The method of claim 1, comprising the additional step of removing some or all of the active agent that is not bound to calcium. 19. The method of claim 1, wherein from about 25 to about 90% normal equivalents of the divalent or polyvalent metal salt of said oxyacid relative to calcium are added during step (b). 20, Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 and R_2 are independently hydrogen or an organic residue of an organic compound having at least one active hydrogen, and X_1 and X_2 are independently are oxygen, sulfur or nitrogen, and M_1, M_2 and M_3 are M_1, M_2 and M_
is independently a divalent or polyvalent metal, with the proviso that at least one of Y_1 is calcium;
and Y_2 are independently divalent or polyvalent oxyacid anions with a valence of 2 to 6, and at least one of Y_1 and Y_2 is a divalent or polyvalent oxyacid anion with a valence of 2 to 6. is oxygen, sulfur or nitrogen, j is an integer having a valence of 0 to about 100, and f and g are such that when j has a value of 0, the sum of f+g equals the valence of Y_1 is an integer with a valence such that f
and g is when j has a value other than 0, the sum of f+g is Y
_1+[M_3-Y_2] is an integer having a valence such that it is equal to the valence of j). 21. An alkoxylation catalyst produced by the method of claim 1. 22. An alkoxylation catalyst produced by the method of claim 14. 23. A process for the alkoxylation of alcohols, which comprises alkoxylating alcohols with alkylene oxides to produce alkoxylates of alcohols under alkoxylation conditions in the presence of the catalyst of claim 20. 24. The method of claim 23, wherein said alcohol comprises a monohydric aliphatic alcohol having from 1 to 7 carbons. 25. The method of claim 24, wherein the monohydric aliphatic alcohol is selected from methanol, 2-methoxyethanol and 2-(2-methoxyethoxy)ethanol. 26. The method of claim 23, wherein said alcohol comprises a dihydric alcohol. 27. The method according to claim 26, wherein the dihydric alcohol is ethylene glycol. 28. The method of claim 23, wherein said alcohol comprises a polyhydric alcohol. 29. Claim 2, wherein the polyhydric alcohol is glycerin.
8. The method described in 8. 30. The method of claim 23, wherein the alkylene oxide is ethylene oxide. 31. The method according to claim 23, wherein the alkylene oxides are ethylene oxide and propylene oxide. 32. The method of claim 23, wherein said alcohol comprises a monohydric aliphatic alcohol having from 8 to 20 carbons. 33, the monohydric aliphatic alcohol is n-dodecanol,
Mixture of C_8~C_10 alcohols and C_1_2~
Claim 3 selected from mixtures of C_1_4 alcohols.
The method described in 2. 34. The method of claim 23, wherein the alcohol is a product of a hydroformylation/hydrogenation reaction. 35. (a) Calcium metal or calcium-containing compound is defined by the formula ▲ mathematical formula, chemical formula, table, etc. ▼ (wherein R_4 and R_5 are the same or different, and hydrogen and lower alkyl having 1 to 4 carbon atoms p is an integer from 2 to 4, X and Y are the same or different electronegative heteroatoms selected from the group consisting of oxygen and nitrogen, and a and b are X
and Y are the same or different integers that satisfy the valence requirements, and Z and Z' are the same or different and are either hydrogen or an organic group that does not interfere with the reaction or solubilization)
(b) optionally heating the calcium-containing composition; (c) reacting the calcium-containing composition with at least one divalent or multivalent metal salt of an oxyacid under effective reaction conditions to form an alkoxylation catalyst; d) stripping away active agents that do not bind to calcium; and (e) reacting said alkoxylation catalyst with a surfactant molecular weight alcohol under conditions in which an alcohol exchange reaction occurs with the alkoxylation catalyst to remove the alkoxylation catalyst. (f) introducing an alkylene oxide under conditions in which an alkoxylation reaction occurs to produce an alkoxylated derivative of the alcohol; and (g) recovering said derivative. A process for producing a nonionic surfactant comprising an alkoxylated derivative of an alcohol, in which steps (d) and (e) are interchangeable in any combination in this process. 36, the calcium-containing compound is an oxide, a hydroxide,
carboxylates, alcoholates, ammonides, amides, nitrides, thiocyanates, thiolates, carbides,
36. A method according to claim 35, selected from thiophenoxides and substances that are converted in situ to said compounds in said method. 37. The method of claim 36, wherein said calcium-containing compound is a carboxylate selected from acetates, formates, oxalates, citrates, benzoates, laurates, stearates and substances that are converted to said compounds in situ in said method. . 38. Claim 35, wherein the calcium-containing compound is calcium oxide, calcium hydroxide, or a mixture thereof.
Method described. 39. The method of claim 35, wherein the calcium-containing compound is a calcium-containing alcoholate. 40. Claim 3, wherein the activator is ethylene glycol.
5. The method described in 5. 41. The method of claim 35, wherein the activator is 2-ethoxyethanol. 42, the alcohol is n-dodecanol or C_1
Claim 35 is a mixture of _2 to C_1_4 alcohols.
Method described. 43. The method of claim 35, wherein the alkylene oxide is ethylene oxide. 44. The method of claim 35, wherein the alcohol is a mixture of C_8 to C_1_0 alcohols. 45. The method according to claim 35, wherein the alkylene oxides are ethylene oxide and propylene oxide. 46. The method of claim 35, wherein the molar ratio of alkylene oxide to active hydrogen is at least about 4. 47. The method of claim 35, wherein the alcohol is a product of a hydroformylation/hydrogenation reaction. 48. The method of claim 35, wherein the divalent or polyvalent metal salt of the oxyacid is a metal sulfate. 49. The method of claim 35, wherein the divalent or polyvalent metal salt of the oxyacid is a metal phosphate. 50, (a) Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 and R_2 are independently hydrogen, or are organic residues of an organic compound having at least one active hydrogen. X_1, X_2, X_3 and X_4 are independently oxygen, sulfur or nitrogen, M_4 is calcium, j is an integer having a valence of 0 to about 100, and f' and g' are If it has a valence of 0, it is an integer with a valence such that the sum of f'+g' is equal to the valence of X_3,
And f' and g' are f' when j has a value other than 0.
+g' is an integer having a valence such that the sum of a valent or polyvalent metal salt under agitation, and the contacting is in a liquid solvent having a dielectric constant of at least about 10 at 25° C. or at the boiling point (whichever is lower). and the divalent or polyvalent metal salt of said oxyacid accounts for at least about 20% of the alkoxylation product mixture.
(b) the organic compound having at least one active hydrogen shall be provided in an amount sufficient to provide an alkoxylated product mixture having at least one alkoxylated species in an amount of 0% by weight; oxide and at least one alkoxylated species comprising at least about 20% by weight of the product mixture in the presence of a catalytically effective amount of a modified alkoxylation catalyst or exchanged derivative thereof. A method for producing an alkoxylated product mixture having a narrow distribution of species with at least one alkoxylate species comprising at least about 20% by weight of the product mixture, comprising contacting under sufficient alkoxylation conditions. . 51. The method of claim 50, wherein the agitation during step (a) is sufficient to ensure that the product is relatively homogeneous. 52. The method of claim 50, wherein step (a) is carried out in the presence of ethylene glycol. 53. The method of claim 50, wherein the modified alkoxylation catalyst is replaced with an alcohol before step (b), and in step (b) the alcohol is alkoxylated with an alkylene oxide comprising ethylene oxide. 54. The method of claim 53, wherein the exchanged alcohol and the alcohol in step (b) are the same. 55, 1 in which the alcohol has about 8 to 20 carbons
55. The method of claim 54, comprising a fatty aliphatic alcohol. 56. The method of claim 55, wherein the molar ratio of ethylene oxide to alcohol in step (b) is about 4 to 16. 57. The method of claim 56, wherein said organic compound having at least one active hydrogen comprises ethylene glycol or diethylene glycol, and said product mixture comprises triethylene glycol and tetraethylene glycol. 58. The method of claim 57, wherein triethylene glycol and tetraethylene glycol account for at least about 75% by weight of said product mixture. 59, wherein the alkoxylated product mixture has at least one alkoxylated component accounting for about 20-40% by weight of the mixture, and wherein the alkoxylated product mixture has at least 3 or more oxyalkylene units than the average peak alkoxylated species. less than about 12% by weight of the mixture and which has more than the most abundant oxyalkylene groups
The alkoxylated species having two oxyalkylene groups and the alkoxylated species having one oxyalkylene group smaller than the oxyalkylene group of the most abundant species in a weight ratio of about 0.6:1 to 1:1 to the most abundant species. 51. The method of claim 50, wherein the method is present. 60, the alkoxylated species having a weight average alkoxylation number in the range of plus or minus 2 range from about 80 to
60. The method of claim 59, comprising 95% by weight. 61. The method of claim 60, wherein the oxyalkylene group consists of oxyethylene. 62. The method of claim 60, wherein the molar ratio of alkylene oxide reacted with active hydrogen is about 4 to 16. 63. The method according to claim 62, wherein the organic compound having active hydrogen is an alcohol. 64, 1 in which the alcohol has about 8 to 20 carbons
64. The method of claim 63, comprising a fatty aliphatic alcohol. 65, the most common alkoxylated species are 4, 5, 6, 7
, 8, 9, 10, 11 or 12 oxyalkylene units. 66. The method of claim 59, wherein said oxyalkylene groups consist of oxyethylene and oxypropylene. 67. The method of claim 63, wherein said alcohol comprises a monohydric aliphatic alcohol having from 1 to 7 carbons. 68. The method of claim 67, wherein the monohydric aliphatic alcohol is selected from methanol, 2-methoxyethanol and 2-(2-methoxyethoxy)ethanol. 69. The method of claim 63, wherein said alcohol comprises a dihydric alcohol. 70. The method of claim 69, wherein the dihydric alcohol is ethylene glycol. 71. The method of claim 63, wherein said alcohol comprises a polyhydric alcohol. 72. Claim 7, wherein the polyhydric alcohol is glycerin.
The method described in 1. 73, the alcohol is n-dodecanol, C_8-C
_1_0 mixture of alcohols and C_1_2 to C_1_
65. The method of claim 64, wherein the alcohol is selected from a mixture of 4 alcohols. 74. The alkoxylated product mixture has the formula ▲ mathematical formula, chemical formula, table, etc. is the number of groups, @n@ is the weight average oxyalkylene number of the mixture, A is the weight percent of the most abundant alkoxylated species in the mixture, and P_π is the number of groups, within plus or minus 2%, of the mixture. 51. The method of claim 50, wherein the method has an alkoxylated species distribution corresponding to % of the alkoxylated species having n oxyalkylene groups per active hydrogen site based on the weight of . 75, the most common alkoxylated species are 4, 5, 6, 7
, 8, 9, 10, 11 or 12 oxyalkylene units. 76. The method of claim 75, wherein said alcohol comprises a dihydric alcohol. 77. The method of claim 76, wherein said dihydric alcohol comprises ethylene glycol. 78. The method of claim 77, wherein said alkylene oxide comprises ethylene oxide. 79. The method of claim 75, wherein said alcohol comprises a monohydric aliphatic alcohol having about 8 to 20 carbon atoms. 80. The method of claim 79, wherein said alkylene oxide comprises ethylene oxide. 81. The method of claim 80, wherein the at least one alkoxylated species comprises about 22-28% by weight of the composition. 82, the most common alkoxylated species is 6, 7 or 3
82. The method of claim 81, having 2 oxyalkylene groups. 83. The method of claim 74, wherein the alkylene oxide is ethylene oxide. 84. The method of claim 74, wherein the alkylene oxides are ethylene oxide and propylene oxide. 85. The method of claim 74, wherein said alcohol comprises a monohydric aliphatic alcohol having from 1 to 70 carbon atoms. 86. The method of claim 85, wherein the monohydric aliphatic alcohol is selected from methanol, 2-methoxyethanol and 2-(2-methoxyethoxy)ethanol. 87. The method of claim 74, wherein said alcohol comprises a polyhydric alcohol. 88. Claim 8, wherein the polyhydric alcohol is glycerin.
7. The method described in 7. 89, the alcohol is n-dodecanol, C_8-C
_1_0 mixture of alcohols and C_1_2 to C_4_
80. The method of claim 79, wherein the alcohol is selected from a mixture of 4 alcohols. 90, the alkoxylated product mixture obtained from the reaction of a monohydric aliphatic alcohol having about 8 to 20 carbon atoms with ethylene oxide and/or propylene oxide has the formula ▲ mathematical formula, chemical formula, table, etc. ▼ (formula where n is at least one integer and is the number of oxyalkylene groups per reactive hydrogen site of the alcohol toward the alkoxylated species, @n@ is the weight average number of oxyalkylenes in the mixture, and A is 6 in the mixture,
is the weight percent of the predominant alkoxylated species with 7, 8, 9, 10, 11 or 12 oxyalkylene groups, and P_n is the active hydrogen site 1 relative to the weight of the mixture, within plus or minus 2%. 50. Claim 50 having an alkoxylated species distribution corresponding to (% by weight of alkoxylated species having n oxyalkylene groups per unit)
Method described. 91, the alkoxylated product mixture obtained from the reaction of a monohydric aliphatic alcohol having about 1 to 7 carbon atoms with ethylene oxide and/or propylene oxide has the formula ▲ mathematical formula, chemical formula, table, etc. ▼ (wherein n is at least one integer and is the number of oxyalkylene groups per reactive hydrogen site of the alcohol toward the alkoxylated species, @n@ is the weight average number of oxyalkylenes in the mixture, and A is the number of oxyalkylene groups in the mixture. 6,
is the weight percent of the predominant alkoxylated species with 7, 8, 9, 10, 11 or 12 oxyalkylene groups, and P_n is the active hydrogen site 1 relative to the weight of the mixture, within plus or minus 2%. 50. Claim 50 having an alkoxylated species distribution corresponding to (% by weight of alkoxylated species having n oxyalkylene groups per unit)
Method described. 92, the alkoxylated product mixture obtained from the reaction of a dihydric aliphatic alcohol having about 1 to 20 carbon atoms with ethylene oxide and/or propylene oxide has the formula ▲ mathematical formula, chemical formula, table, etc. ▼ (formula where n is at least one integer and is the number of oxyalkylene groups per reactive hydrogen site of the alcohol toward the alkoxylated species, @n@ is the weight average number of oxyalkylenes in the mixture, and A is 6 in the mixture,
is the weight percent of the predominant alkoxylated species with 7, 8, 9, 10, 11 or 12 oxyalkylene groups, and P_n is the active hydrogen site 1 relative to the weight of the mixture, within plus or minus 2%. (% by weight of alkoxylated species having n oxyalkylene groups per unit)
51. The method of claim 50, having an alkoxylation species distribution corresponding to , and wherein the alkoxylation product mixture contains a negligible amount of catalyst residue. 93, the alkoxylated product mixture obtained from the reaction of a polyhydric alcohol having about 1 to 20 carbon atoms with ethylene oxide and/or propylene oxide has the formula ▲ mathematical formula, chemical formula, table, etc. ▼ (wherein n is at least one integer and is the number of oxyalkylene groups per reactive hydrogen site of the alcohol toward the alkoxylated species, @n@ is the weight average number of oxyalkylenes in the mixture, and A is the number of oxyalkylene groups in the mixture. 6,
is the weight percent of the predominant alkoxylated species with 7, 8, 9, 10, 11 or 12 oxyalkylene groups, and P_n is the active hydrogen site 1 relative to the weight of the mixture, within plus or minus 2%. 50. Claim 50 having an alkoxylated species distribution corresponding to (% by weight of alkoxylated species having n oxyalkylene groups per unit)
Method described.