CA2040834A1 - Process for the preparation of alkoxylates having a narrow homolog distribution - Google Patents
Process for the preparation of alkoxylates having a narrow homolog distributionInfo
- Publication number
- CA2040834A1 CA2040834A1 CA002040834A CA2040834A CA2040834A1 CA 2040834 A1 CA2040834 A1 CA 2040834A1 CA 002040834 A CA002040834 A CA 002040834A CA 2040834 A CA2040834 A CA 2040834A CA 2040834 A1 CA2040834 A1 CA 2040834A1
- Authority
- CA
- Canada
- Prior art keywords
- mol
- catalyst
- antimony
- amount
- premixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/04—Formation or introduction of functional groups containing oxygen of ether, acetal or ketal groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Abstract of the disclosure Process for the preparation of alkoxylates having a narrow homolog distribution In the process described, the alkoxylation of compounds containing active hydrogen atoms is carried out using antimony pentahalides as catalyst by first preparing a catalyst premixture by dissolving antimony pentahalide in a partial amount of the compound intended for alkoxyla-tion while maintaining a temperature of at most 60°C and a concentration of antimony pentahalide of at most 30 mol %, combining the prepared catalyst premixture or a part thereof as a catalyst component with the residual amount of the compound to be alkoxylated and reacting the starting mixture thus obtained with the alkylene oxide.
Description
2~ 33~
HOECHST AKTIENGESELLSCHAFT HOE 90/F 905 Dr.GL-nu Werk Gendorf Process for the preparation of alkoxylates having a narrow homolog distribution Description The invention relates to a proce s for the preparation of alkoxylates having a narrow homolog distri~ution by reaction of compounds containing at least one active hydrogen atom with an alkylene oxide using antimony pentahalides as catalyst.
Alkoxylation processes of this type have already been known for a long time, for example from British Patent No. 796,508 and US Patent No. 3,359,331. In the process of the British patent, the compound to be alkoxylated and the antimony pentahalide are initially introduced as such into a reaction vessel, after which the mixture is react~d with alkylene oxide at reaction temperature. The alkoxylate ob~ained indeed has a relatively narrow homolog distribution, i.e. so-called 'narrow-range"
alkoxylates, however, it leaves something to be desired, in particular with respect to color and content of by-products. A disadvantage of the known process is further-more that, owing to the use of the antimony pentahalide in sub~tance, its corrosiveness and problematical hand-ling occur to a particularly large extent. These di~ad-vantages are indicated in said US Patent No. 3,359,331 (column 1, lines 27 to 54). To avoid them~ the alkoxyla-tion is caxried out by first preparing a premixture by only reacting a part of the intended amounts of catalyst, alkoxylating compound and alkylene oxide in a reaction vessel made of glass, ceramics and the like. This premixture (seed product) is then combined with the residual amounts of catalyst, alkoxylating compound and alkylene oxide in a reaction vessel made of metal, after - 2 - 2~ 8~'&
which the mixture is further alkoxylated. It is obvious that this proces~ is troublesome and leads to alkoxylates which have a broader homolog di5tribution than would be expected with antimony pentahalide as the catalyst.
The object of the invention is to make available a process for the alkoxylation of compounds containing active hydrogen atoms using antimony pentahalides, which does not have said disadvantages, but on the other hand utilizes the advantageous property of antimony penta-halides, namely the formation of "narrow-range" alkoxy-lates. The novel process should thus offer relatively problem-free handling of antimony pentahalides in the context of the alkoxylation and yield alkoxylates in high yield, which not only have a narrow homolog di6tribution, but also a good color quality.
The process according to the invention comprises a) preparing a catalyst premixture containing at most 30 mol %, relative to the amount of compound employ-ed, of antimony pentahalide containing a partial amount of the compound intended for alkoxylation, by dissolving antimony pentahalide in the amount of compound employed while maintaining a temperature of at most 60C and said concentration of antimony pentahalide of at most 30 mol %, and b) employing this premixture as a catalyst component by combining the entire premixture prepared or a part thereof with the residual amount of the com-pound to be aIkoxylated, and c) reacting the starting mixture thus obtained with the alkylene oxide, with the proviso that an amount of antimony pentahalide of 0.05 to 1 mol % is present in the starting mixture, pxeferably 0.2 to 0.6 mol ~, relative to the`amount of compound to be alkoxylated.
The process according to the invention differs from the prior art according to said British Patent No.796,508 in that the antimony pentahalide is not employed as such, - 3 - 20flOB3~
but in the form of a specific solution in the compound to be alkoxylated, and from the prior art according to said US Patent No. 3,359,331 in that alkylene oxide i5 not involved in the p~eparation o~ the catalyst premixture.
In the process according to the invention, a part of the amount of compound intended for alkoxylation and the antimony pentahalide present in substance and to be employed as catalyst are thug mixed in a first step lStep a)] to give a solution. On mixing, a temperature of 60C
should not be exceeded and in addition the concentration of the antLmony pentahalide in the solution ~hould be brought to at most 30 mol ~. At a temperature of more than 60C in the course of the exothermic solution reac-tion, the risk of color ~ormation exists. If low ~emper-atures are also not critical, the dissolution process is not carried out below 20C for reasons of expediency.
The preferred dissolution temperature is accordingly 20 to 60C. If the concentration of the antimony pentahali-de in the solution is brought to over 30 mol ~, there islikewise the risk of color foxmation. ~ow catalyst concentrations, on the other hand, are not expedient. For these reasons, the concentration in question is adjusted to a value of 5 to 30 mol %, preferably to 10 to 20 mol ~, molar percentages relative to the amount employed (partial amount) of compound to be alkoxylated. As far as the amount of prepared catalyst premixture is con-cerned, this is not critical for the process according to the invention. As a rul~, an amount of premixture is prepared such that with it not only one, but several (separated to a greater or lesser extent chronologically) alkoxylations can be carried out, a part o~ the catalyst premixture being employed each time, in par~icular a - quantity such that the antimony pentahalide concentration indicated is present in the starting mixtuxe. Starting from the case in which a specified amount of compound (product) is present which i5 intended to be alko~ylated, about 1 to about 20 ~ by weight thereof, preferably 1 to 10~ by weight, is used for the preparation of the - 4 ~ 8~
catalyst pr~mi~ure. The mixing of the two components i8 preferably carried out by initially introducing the compound and adding the antimony pentahalide to it in portions or continuously, preferably continuously, with stirring and maintenance of the temperature indicated, if appropriate by cooling. The solution obtained, which is relatively concentrated $n antLmony pentahalide, i~ the desired catalyst premixture (catalyst component).
In the second step [Step b)~ of the process according to the invention, the prepared antimony pentahalide premix-ture and the residual amount of the compound to be alkoxylated are brought together. The process of bring-ing together is preferably carried out with s~irring in order to achieve good mixing. The mixing temperature can vary within wide lLmits, and it is preferably 20 to 80C.
The two parts can be combined such that the catalyst premixture is added to the residual amount (in portions or continuously) or the residual amount to the catalyst premixture. The mixture thus obtained (solution) is the startin~ ~ixture to be alkoxylated. As already men-tioned, the entire prepared catalyst premixture or only a part thereof can be employed in Step b), where care is to be taken in each case that an effective amount of catalyst is also pxesent in the starting mixture, i.e.
an amount of antimony pentahalide of at least 0.05 mol ~, preferably of at least of 0.2 mol %, molar percentages relative to the molar amoun~ of the compound to be alkoxylated. With less than 0.05 mol %, the alkoxylation reaction already proceed~ very slowly, and with more than 1 mol ~, color and by-product formation may already occur. The amount of catalyst i8 thus in the range from 0.05 to 1 mol ~, preferably 0.2 to 0.6 mol %, molar percentages relative to the molar amount of compound to be alkoxylated.
In the third step [Step c)] of the process according to the invention, the starting mixture obtained is alkoxylated in a customary manner, i.e. reacted with the ~ 5 - % ~ ~83 selected alkylene oxide. The alkoxylation is thus preferably carried out by bringing the s~arting mixture to a temperature of 40 to 160C, preferably 60 to 140C, with stirring and metering in the alkylene oxide in portions or continuously while maintaining said tempera-ture. During the reaction, normal pressure or an elevated pressure can be present. A8 a rule, the alkoxylation is carried out at a pressure of 2 to 6 bar.
After completion of addition of the alkylenc oxide, the mixture is still kept at the said temperature for some tLme for the subsequent reaction, the pressure falling more and more and indicating the end of the reaction.
The amount of alkylene oxide depends on the purpose for which the alkoxylate is employed and is in general l ~o 30 mol, preferably 2 to 15 mol and in particular 2 to 8 mol, per mol of compound to be alkoxylated. The rea~tion product obtained can often already be employed as such, i.e. without removal of the catalyst.
In the case in which it is intended ~o obtain a catalyst-free alkoxylate, the reaction product can be treated, for example, with water or alkali to destroy the catalyst, after which the organic phase (i.e. the desired alkoxy-late) is separated from the aqueous phase.
The process according to the invention yields alkoxylates in high yield, which not only have a narrow homolog distribution, but also a good color quality. They can therefore also be used where color quality is particu-larly important. The process according to the inventionadditionally offers simple and problem-free handlin~ of antimony pentahalide with re~pect to its use and its metering in industrial alkoxylation processes owing to the prepared, relatively concentrated catalyst premix-ture. The concentrated catalyst premixture prepared inthe process according to the in~ention is non-fuming at room temperature or below and can be kept for a relat-ively lon~ time without losse~ in activity, so it can also be used for several alkoxylations.
- 6 - 2~ 3~
If the type of the components, alkylene oxide, antimony pentahalide and compound containing active hydrogen atoms present in the process according to the invention i5 also not critical, the following may be set out for this purpose:
Alkylene oxides employed are pre~erably ethylene oxide, propylene oxide and/or butylene oxide, ethylene oxide and~or propylene oxide being preferred. Ethylene oxide i8 particularly prefexred.
The antimony pentahalide employed is preferably antimony pentabromide or antLmony pentachloride, the la~ter being preferred.
Suitable compounds containing active hydrogen atoms are not only compounds containing hydroxyl groups, but also amines, amides, acids, phenols, cresols and the like, where, however, the former are prefexred. Of the com-pounds containing hydroxyl groups, the alcohols, amino alcohols, glycols, glycol monoethers, glycerol and the like may be mentioned, the alcohols being preferred.
They can originate from a natural source or from syn-thesis processes, and in particular can be prLmary or secondary, linear or branched, mono- or polyhydric, for example oxo alcohols, Guerbet alcohols, Ziegler alcohols, fatty alcohols and the like. Preferred alcohols are the primary and straight chain or branched C3 to Cz4-alkanols, preferably C6 to C18-alkanols. Examples of the preferred alcohols which may be mentioned are~ butanol, amyl alcohol, hexanol, nonanol, isonon~l alcohol, decanol, lauryl alcohol, isotridecyl alcohol, stearyl alcohol, coconut fatty alcohol and mixtures thereof, ~uch as C12 to C14-alkanol mixtures, and in addition 2-ethylhexanol, 2-hexyldecanol, 2-octyldecanol and ~Lmilar Guerbet al-cohols.
The invention will now addi~ionally be illustrated inmore detail by examples.
2(~3133f~
Example 1 731 g (3.75 mol) of a straight-chain Cl2 to C14-alkanol mixture were to be alkoxylated with 660 g (14.9 mol) of ethylene oxide using 0.30 mol ~ of antimony pentachloride as the catalyst, i.e. 3.4 g (0.0114 mol) of antimony pentachloride.
An antimony pentachloride premixture was first prepared in which the total intended amount of SbC15, i.e. said 3.4 g, and 7.3 g (0.037 mol) of alkanol mixture, iOe. 1~
by weight, were employed. The preparation of the premix-ture under dry nitrogen as a protective gas was carried out by introducing the 3.4 g of SbC15 continuously with stirring and maintenance of a temperature of 30 to 50C
into the 7.3 g of n-Cl2 to C14-alcohol. ~he premixture (10.7 g) obtained, which did not fume in air, had a concentration of 30 mol % of SbC15, relative to the molar amount of alkanol.
The 10.7 g of catalyst premixture, i.e. the total premix-ture prepared, and the residual amount of alkanol mix-ture, i.e. 723.7 g, were then mixed with stirring at 70 to 80C. The starting mixture obtained comprised 3.4 g (0.0114 mol) of SbCl5 and 731 g (3.75 mol) of n-C12 to C14-alcohol and contained 0.30 mol % of SbCls, relative to the total amount of alkanol.
The ethoxylation of the starting mixture was carried out in a 3 liter stirred autoclave. To do thi~, the mixture was heated to 80C. 660 g of gaseous ethylene oxide (15.0 mol) were added to the heated starting mixture with stirring and at a temperature of 80 to 120C at the rate at which it reacted. The pressure in the autoclave was 2 to 3 bar. After the total amount of ethylene oxide had been metered in, the mixture was stirred for a further 2 hours at 120C for subsequent reaction, after which the pressure remained constant at 0.8 bar and indicated the end of the reaction. 20 g of a 10~ strength by weight - 8 ~
aqueous NaOH solution were added to the content of the autoclave (the reaction product) to destroy the catalyst, the mixtur~ was stirred at 90C for 0.5 hour~ and ~he aqueous phase was then separated from the organic phase.
The Cl2 to C,4-alkanol alko~ylate obtained having, in the statistical mean, 4 mol of ethylene oxide/mol and a narrow homolog dis~ribution was obtained in virtually quantitative yield snd had a Hazen (~.P.~.A.) color number of 120, measured according to DIN 53 409.
Examples 2 to 6 These examples are summarised in the table below. The table also contains Example 1 for ~he sake of complete-ness.
Of the compounds to be alkoxyla~ed in Examples 2 to 6, a catalyst premixture was in each case prepared by dissolv-ing the indicated number of grams of SbC15 in the indi-cated n~nber of grams of alcohol while maintaining the mixing temperature indicated. Usiny ~he premixture obtained and the alcohol in question, the ~tartîng mixture was prepared by mixing the two components as in Example 1, i.e. at 70 to 80C, the total catalyst premix-ture prepared being employed in Examples 2 ~o 4 and only a part thereof being employed in Examples 5 and 6. The alkoxylation of the starting mixtures was also carried out as in Example 1 using the conditions indicated in the table. As far as the results of Examples 2 to 6 are concerned, in this ca~e also a virtually quantitative yield and a narrow homolcg distribution were obtained;
the color of the alkoxylates i8 indicated in the table.
Comparison example Example 1 was repeated with the dif~erence that the SbCl5 was not employed in the form of the premixture described, - 9 - 2~408~
but as such. It was thus carried out by initially introducing the 731 g (3.75 mol~ of the Cl2 to C14-alkanol mixture into the 3-liter stirred autoclave and introd~c-in~ ~he 3.4 g (0.0114 mol) of antimony pentachloride into the initially introduced alcohol, which was at room temperature, with stirring, after which the mixture was ethoxylated, as in Example 1, with the 660 g ~15.0 mol) of ethylene oxide.
The C~2 to C14-alkanol alkoxylate obtained having, in the statistical mean, 4 mol of ethylene oxide/mol al~o showed the narrow homolog distribution typical for SbC15 cataly-sis. Its Hazen color number was 300, i.e. this alkoxy-late was distinctly more strongly colored than the alkoxylates of the examples according to the invention.
_._ I ~ o ~,,, o o o o o o o I ~ I
' a~ ~ ~ s , o o o ~ o o I ~ o , ' ~
u~ o ~1 , U~ ~ l ~ ~ o _~ o o I ~
h rl I ~
o~ ` o ~ o t~
I ,, o ~ I ~' ~ ~ ~ o 1 ~ I
~u ,, ~ r~
I U ~ D
~ l ~:C ~ I N ~ ~ ~ 9 - -~ a) ,_ I O c: o o c~
~ ~ 8 ~ o~, ~ ~ I
a~ ~ O I
_ ~ ~o u u ~, e ~
~ ~ ~ I
~, tn ~ ' ~
~ I
.-I, '~
n~ ~ I O ~O O --~ O O
O O j ~ O O O O
l~
~I
~ j ~ 11 ~O~OO
~1 o tl~ l o u~ U ~I 1` u~
O _ ~ I
~ ~ ~ I
P~ ~ ~ I
.~1 ~ ~ ~ I
~ ~ ~ ~ I
O U~ ~ O
li3 ~ ao ~ i ~q ~ ~ I
cn~ I
HOECHST AKTIENGESELLSCHAFT HOE 90/F 905 Dr.GL-nu Werk Gendorf Process for the preparation of alkoxylates having a narrow homolog distribution Description The invention relates to a proce s for the preparation of alkoxylates having a narrow homolog distri~ution by reaction of compounds containing at least one active hydrogen atom with an alkylene oxide using antimony pentahalides as catalyst.
Alkoxylation processes of this type have already been known for a long time, for example from British Patent No. 796,508 and US Patent No. 3,359,331. In the process of the British patent, the compound to be alkoxylated and the antimony pentahalide are initially introduced as such into a reaction vessel, after which the mixture is react~d with alkylene oxide at reaction temperature. The alkoxylate ob~ained indeed has a relatively narrow homolog distribution, i.e. so-called 'narrow-range"
alkoxylates, however, it leaves something to be desired, in particular with respect to color and content of by-products. A disadvantage of the known process is further-more that, owing to the use of the antimony pentahalide in sub~tance, its corrosiveness and problematical hand-ling occur to a particularly large extent. These di~ad-vantages are indicated in said US Patent No. 3,359,331 (column 1, lines 27 to 54). To avoid them~ the alkoxyla-tion is caxried out by first preparing a premixture by only reacting a part of the intended amounts of catalyst, alkoxylating compound and alkylene oxide in a reaction vessel made of glass, ceramics and the like. This premixture (seed product) is then combined with the residual amounts of catalyst, alkoxylating compound and alkylene oxide in a reaction vessel made of metal, after - 2 - 2~ 8~'&
which the mixture is further alkoxylated. It is obvious that this proces~ is troublesome and leads to alkoxylates which have a broader homolog di5tribution than would be expected with antimony pentahalide as the catalyst.
The object of the invention is to make available a process for the alkoxylation of compounds containing active hydrogen atoms using antimony pentahalides, which does not have said disadvantages, but on the other hand utilizes the advantageous property of antimony penta-halides, namely the formation of "narrow-range" alkoxy-lates. The novel process should thus offer relatively problem-free handling of antimony pentahalides in the context of the alkoxylation and yield alkoxylates in high yield, which not only have a narrow homolog di6tribution, but also a good color quality.
The process according to the invention comprises a) preparing a catalyst premixture containing at most 30 mol %, relative to the amount of compound employ-ed, of antimony pentahalide containing a partial amount of the compound intended for alkoxylation, by dissolving antimony pentahalide in the amount of compound employed while maintaining a temperature of at most 60C and said concentration of antimony pentahalide of at most 30 mol %, and b) employing this premixture as a catalyst component by combining the entire premixture prepared or a part thereof with the residual amount of the com-pound to be aIkoxylated, and c) reacting the starting mixture thus obtained with the alkylene oxide, with the proviso that an amount of antimony pentahalide of 0.05 to 1 mol % is present in the starting mixture, pxeferably 0.2 to 0.6 mol ~, relative to the`amount of compound to be alkoxylated.
The process according to the invention differs from the prior art according to said British Patent No.796,508 in that the antimony pentahalide is not employed as such, - 3 - 20flOB3~
but in the form of a specific solution in the compound to be alkoxylated, and from the prior art according to said US Patent No. 3,359,331 in that alkylene oxide i5 not involved in the p~eparation o~ the catalyst premixture.
In the process according to the invention, a part of the amount of compound intended for alkoxylation and the antimony pentahalide present in substance and to be employed as catalyst are thug mixed in a first step lStep a)] to give a solution. On mixing, a temperature of 60C
should not be exceeded and in addition the concentration of the antLmony pentahalide in the solution ~hould be brought to at most 30 mol ~. At a temperature of more than 60C in the course of the exothermic solution reac-tion, the risk of color ~ormation exists. If low ~emper-atures are also not critical, the dissolution process is not carried out below 20C for reasons of expediency.
The preferred dissolution temperature is accordingly 20 to 60C. If the concentration of the antimony pentahali-de in the solution is brought to over 30 mol ~, there islikewise the risk of color foxmation. ~ow catalyst concentrations, on the other hand, are not expedient. For these reasons, the concentration in question is adjusted to a value of 5 to 30 mol %, preferably to 10 to 20 mol ~, molar percentages relative to the amount employed (partial amount) of compound to be alkoxylated. As far as the amount of prepared catalyst premixture is con-cerned, this is not critical for the process according to the invention. As a rul~, an amount of premixture is prepared such that with it not only one, but several (separated to a greater or lesser extent chronologically) alkoxylations can be carried out, a part o~ the catalyst premixture being employed each time, in par~icular a - quantity such that the antimony pentahalide concentration indicated is present in the starting mixtuxe. Starting from the case in which a specified amount of compound (product) is present which i5 intended to be alko~ylated, about 1 to about 20 ~ by weight thereof, preferably 1 to 10~ by weight, is used for the preparation of the - 4 ~ 8~
catalyst pr~mi~ure. The mixing of the two components i8 preferably carried out by initially introducing the compound and adding the antimony pentahalide to it in portions or continuously, preferably continuously, with stirring and maintenance of the temperature indicated, if appropriate by cooling. The solution obtained, which is relatively concentrated $n antLmony pentahalide, i~ the desired catalyst premixture (catalyst component).
In the second step [Step b)~ of the process according to the invention, the prepared antimony pentahalide premix-ture and the residual amount of the compound to be alkoxylated are brought together. The process of bring-ing together is preferably carried out with s~irring in order to achieve good mixing. The mixing temperature can vary within wide lLmits, and it is preferably 20 to 80C.
The two parts can be combined such that the catalyst premixture is added to the residual amount (in portions or continuously) or the residual amount to the catalyst premixture. The mixture thus obtained (solution) is the startin~ ~ixture to be alkoxylated. As already men-tioned, the entire prepared catalyst premixture or only a part thereof can be employed in Step b), where care is to be taken in each case that an effective amount of catalyst is also pxesent in the starting mixture, i.e.
an amount of antimony pentahalide of at least 0.05 mol ~, preferably of at least of 0.2 mol %, molar percentages relative to the molar amoun~ of the compound to be alkoxylated. With less than 0.05 mol %, the alkoxylation reaction already proceed~ very slowly, and with more than 1 mol ~, color and by-product formation may already occur. The amount of catalyst i8 thus in the range from 0.05 to 1 mol ~, preferably 0.2 to 0.6 mol %, molar percentages relative to the molar amount of compound to be alkoxylated.
In the third step [Step c)] of the process according to the invention, the starting mixture obtained is alkoxylated in a customary manner, i.e. reacted with the ~ 5 - % ~ ~83 selected alkylene oxide. The alkoxylation is thus preferably carried out by bringing the s~arting mixture to a temperature of 40 to 160C, preferably 60 to 140C, with stirring and metering in the alkylene oxide in portions or continuously while maintaining said tempera-ture. During the reaction, normal pressure or an elevated pressure can be present. A8 a rule, the alkoxylation is carried out at a pressure of 2 to 6 bar.
After completion of addition of the alkylenc oxide, the mixture is still kept at the said temperature for some tLme for the subsequent reaction, the pressure falling more and more and indicating the end of the reaction.
The amount of alkylene oxide depends on the purpose for which the alkoxylate is employed and is in general l ~o 30 mol, preferably 2 to 15 mol and in particular 2 to 8 mol, per mol of compound to be alkoxylated. The rea~tion product obtained can often already be employed as such, i.e. without removal of the catalyst.
In the case in which it is intended ~o obtain a catalyst-free alkoxylate, the reaction product can be treated, for example, with water or alkali to destroy the catalyst, after which the organic phase (i.e. the desired alkoxy-late) is separated from the aqueous phase.
The process according to the invention yields alkoxylates in high yield, which not only have a narrow homolog distribution, but also a good color quality. They can therefore also be used where color quality is particu-larly important. The process according to the inventionadditionally offers simple and problem-free handlin~ of antimony pentahalide with re~pect to its use and its metering in industrial alkoxylation processes owing to the prepared, relatively concentrated catalyst premix-ture. The concentrated catalyst premixture prepared inthe process according to the in~ention is non-fuming at room temperature or below and can be kept for a relat-ively lon~ time without losse~ in activity, so it can also be used for several alkoxylations.
- 6 - 2~ 3~
If the type of the components, alkylene oxide, antimony pentahalide and compound containing active hydrogen atoms present in the process according to the invention i5 also not critical, the following may be set out for this purpose:
Alkylene oxides employed are pre~erably ethylene oxide, propylene oxide and/or butylene oxide, ethylene oxide and~or propylene oxide being preferred. Ethylene oxide i8 particularly prefexred.
The antimony pentahalide employed is preferably antimony pentabromide or antLmony pentachloride, the la~ter being preferred.
Suitable compounds containing active hydrogen atoms are not only compounds containing hydroxyl groups, but also amines, amides, acids, phenols, cresols and the like, where, however, the former are prefexred. Of the com-pounds containing hydroxyl groups, the alcohols, amino alcohols, glycols, glycol monoethers, glycerol and the like may be mentioned, the alcohols being preferred.
They can originate from a natural source or from syn-thesis processes, and in particular can be prLmary or secondary, linear or branched, mono- or polyhydric, for example oxo alcohols, Guerbet alcohols, Ziegler alcohols, fatty alcohols and the like. Preferred alcohols are the primary and straight chain or branched C3 to Cz4-alkanols, preferably C6 to C18-alkanols. Examples of the preferred alcohols which may be mentioned are~ butanol, amyl alcohol, hexanol, nonanol, isonon~l alcohol, decanol, lauryl alcohol, isotridecyl alcohol, stearyl alcohol, coconut fatty alcohol and mixtures thereof, ~uch as C12 to C14-alkanol mixtures, and in addition 2-ethylhexanol, 2-hexyldecanol, 2-octyldecanol and ~Lmilar Guerbet al-cohols.
The invention will now addi~ionally be illustrated inmore detail by examples.
2(~3133f~
Example 1 731 g (3.75 mol) of a straight-chain Cl2 to C14-alkanol mixture were to be alkoxylated with 660 g (14.9 mol) of ethylene oxide using 0.30 mol ~ of antimony pentachloride as the catalyst, i.e. 3.4 g (0.0114 mol) of antimony pentachloride.
An antimony pentachloride premixture was first prepared in which the total intended amount of SbC15, i.e. said 3.4 g, and 7.3 g (0.037 mol) of alkanol mixture, iOe. 1~
by weight, were employed. The preparation of the premix-ture under dry nitrogen as a protective gas was carried out by introducing the 3.4 g of SbC15 continuously with stirring and maintenance of a temperature of 30 to 50C
into the 7.3 g of n-Cl2 to C14-alcohol. ~he premixture (10.7 g) obtained, which did not fume in air, had a concentration of 30 mol % of SbC15, relative to the molar amount of alkanol.
The 10.7 g of catalyst premixture, i.e. the total premix-ture prepared, and the residual amount of alkanol mix-ture, i.e. 723.7 g, were then mixed with stirring at 70 to 80C. The starting mixture obtained comprised 3.4 g (0.0114 mol) of SbCl5 and 731 g (3.75 mol) of n-C12 to C14-alcohol and contained 0.30 mol % of SbCls, relative to the total amount of alkanol.
The ethoxylation of the starting mixture was carried out in a 3 liter stirred autoclave. To do thi~, the mixture was heated to 80C. 660 g of gaseous ethylene oxide (15.0 mol) were added to the heated starting mixture with stirring and at a temperature of 80 to 120C at the rate at which it reacted. The pressure in the autoclave was 2 to 3 bar. After the total amount of ethylene oxide had been metered in, the mixture was stirred for a further 2 hours at 120C for subsequent reaction, after which the pressure remained constant at 0.8 bar and indicated the end of the reaction. 20 g of a 10~ strength by weight - 8 ~
aqueous NaOH solution were added to the content of the autoclave (the reaction product) to destroy the catalyst, the mixtur~ was stirred at 90C for 0.5 hour~ and ~he aqueous phase was then separated from the organic phase.
The Cl2 to C,4-alkanol alko~ylate obtained having, in the statistical mean, 4 mol of ethylene oxide/mol and a narrow homolog dis~ribution was obtained in virtually quantitative yield snd had a Hazen (~.P.~.A.) color number of 120, measured according to DIN 53 409.
Examples 2 to 6 These examples are summarised in the table below. The table also contains Example 1 for ~he sake of complete-ness.
Of the compounds to be alkoxyla~ed in Examples 2 to 6, a catalyst premixture was in each case prepared by dissolv-ing the indicated number of grams of SbC15 in the indi-cated n~nber of grams of alcohol while maintaining the mixing temperature indicated. Usiny ~he premixture obtained and the alcohol in question, the ~tartîng mixture was prepared by mixing the two components as in Example 1, i.e. at 70 to 80C, the total catalyst premix-ture prepared being employed in Examples 2 ~o 4 and only a part thereof being employed in Examples 5 and 6. The alkoxylation of the starting mixtures was also carried out as in Example 1 using the conditions indicated in the table. As far as the results of Examples 2 to 6 are concerned, in this ca~e also a virtually quantitative yield and a narrow homolcg distribution were obtained;
the color of the alkoxylates i8 indicated in the table.
Comparison example Example 1 was repeated with the dif~erence that the SbCl5 was not employed in the form of the premixture described, - 9 - 2~408~
but as such. It was thus carried out by initially introducing the 731 g (3.75 mol~ of the Cl2 to C14-alkanol mixture into the 3-liter stirred autoclave and introd~c-in~ ~he 3.4 g (0.0114 mol) of antimony pentachloride into the initially introduced alcohol, which was at room temperature, with stirring, after which the mixture was ethoxylated, as in Example 1, with the 660 g ~15.0 mol) of ethylene oxide.
The C~2 to C14-alkanol alkoxylate obtained having, in the statistical mean, 4 mol of ethylene oxide/mol al~o showed the narrow homolog distribution typical for SbC15 cataly-sis. Its Hazen color number was 300, i.e. this alkoxy-late was distinctly more strongly colored than the alkoxylates of the examples according to the invention.
_._ I ~ o ~,,, o o o o o o o I ~ I
' a~ ~ ~ s , o o o ~ o o I ~ o , ' ~
u~ o ~1 , U~ ~ l ~ ~ o _~ o o I ~
h rl I ~
o~ ` o ~ o t~
I ,, o ~ I ~' ~ ~ ~ o 1 ~ I
~u ,, ~ r~
I U ~ D
~ l ~:C ~ I N ~ ~ ~ 9 - -~ a) ,_ I O c: o o c~
~ ~ 8 ~ o~, ~ ~ I
a~ ~ O I
_ ~ ~o u u ~, e ~
~ ~ ~ I
~, tn ~ ' ~
~ I
.-I, '~
n~ ~ I O ~O O --~ O O
O O j ~ O O O O
l~
~I
~ j ~ 11 ~O~OO
~1 o tl~ l o u~ U ~I 1` u~
O _ ~ I
~ ~ ~ I
P~ ~ ~ I
.~1 ~ ~ ~ I
~ ~ ~ ~ I
O U~ ~ O
li3 ~ ao ~ i ~q ~ ~ I
cn~ I
Claims (6)
1. A process for the preparation of alkoxylates having a narrow homolog distribution by reaction of compounds containing at least one active hydrogen atom with an alkylene oxide using antimony pentahalides as catalyst, which comprises a) preparing a catalyst premixture containing at most 30 mol %, relative to the amount of compound employ-ed, of antimony pentahalide containing a partial amount of the compound intended for alkoxylation, by dissolving antimony pentahalide in the amount of compound employed while maintaining a temperature of at most 60°C and said concentration of antimony pentahalide of at most 30 mol %, and b) employing this premixture as a catalyst component by combining the entire premixture prepared or a part thereof with the residual amount of the com-pound to be alkoxylated, and c) reacting the starting mixture thus obtained with the alkylene oxide, with the proviso that an amount of antimony pentahalide of 0.05 to 1 mol % is present in the starting mixture, relative to the amount of compound to be alkoxylated.
2. The process as claimed in claim 1, wherein a catalyst premixture containing 5 to 30 mol % of antimony pentahalide is prepared.
3. The process as claimed in claim 1, wherein a catalyst premixture containing 10 to 20 mol % of antimony pentahalide is prepared.
4. The process as claimed in claim 1, wherein a temperature of 20 to 60°C is maintained while dissolving the antimony pentahalide.
5. The process as claimed in claim 1, wherein an amount of antimony pentahalide of 0.2 to 0.6 mol % is present in the starting mixture.
6. The process as claimed in claim 1, wherein antimony pentachloride is employed as the catalyst, ethylene oxide or propylene oxide is employed as the alkylene oxide and straight-chain or branched primary C6 to C18-alkanols are employed as compounds containing active hydrogen atoms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4012725.7 | 1990-04-21 | ||
| DE4012725A DE4012725A1 (en) | 1990-04-21 | 1990-04-21 | METHOD FOR PRODUCING ALKOXYLATES WITH A NARROW HOMOLOGICAL DISTRIBUTION |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2040834A1 true CA2040834A1 (en) | 1991-10-22 |
Family
ID=6404796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002040834A Abandoned CA2040834A1 (en) | 1990-04-21 | 1991-04-19 | Process for the preparation of alkoxylates having a narrow homolog distribution |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0453967A1 (en) |
| JP (1) | JPH04224540A (en) |
| KR (1) | KR910018331A (en) |
| AU (1) | AU7515591A (en) |
| BR (1) | BR9101578A (en) |
| CA (1) | CA2040834A1 (en) |
| DE (1) | DE4012725A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6455459B1 (en) | 1999-11-18 | 2002-09-24 | Union Carbide Chemicals & Plastics Technology Corporation | Antimony catalyst compositions |
| AU4709601A (en) * | 2000-11-30 | 2002-06-11 | Union Carbide Chem Plastic | Novel antimony catalyst compositions |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB796508A (en) * | 1954-09-01 | 1958-06-11 | Henkel & Cie Gmbh | A process for the reaction of organic compounds containing hydroxyl groups with ethylene oxide |
| US3359331A (en) * | 1965-11-10 | 1967-12-19 | Exxon Research Engineering Co | Secondary alcohol ethoxylation |
-
1990
- 1990-04-21 DE DE4012725A patent/DE4012725A1/en not_active Withdrawn
-
1991
- 1991-04-17 JP JP3085467A patent/JPH04224540A/en not_active Withdrawn
- 1991-04-18 EP EP91106266A patent/EP0453967A1/en not_active Withdrawn
- 1991-04-19 CA CA002040834A patent/CA2040834A1/en not_active Abandoned
- 1991-04-19 BR BR919101578A patent/BR9101578A/en unknown
- 1991-04-19 KR KR1019910006249A patent/KR910018331A/en not_active Application Discontinuation
- 1991-04-19 AU AU75155/91A patent/AU7515591A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| AU7515591A (en) | 1991-10-24 |
| KR910018331A (en) | 1991-11-30 |
| DE4012725A1 (en) | 1991-10-24 |
| BR9101578A (en) | 1991-12-10 |
| EP0453967A1 (en) | 1991-10-30 |
| JPH04224540A (en) | 1992-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0115084B1 (en) | Process for preparing nonionic surfactants by oxyalkylation with promoted barium catalysts | |
| EP0092256B1 (en) | Process for preparing nonionic surfactants by an oxyalkylation with calcium and/or strontium catalysts | |
| EP0273521B1 (en) | A process for the preparation of an alkanol akoxylate product | |
| EP0104309B1 (en) | Catalysts for alkoxylation reactions | |
| EP0046582B1 (en) | Inorganic catalyst for alkoxylation of alcohols | |
| JPS6332055B2 (en) | ||
| EP0033359B1 (en) | A method for the alkoxylation of alkanols | |
| JPS6332054B2 (en) | ||
| JPH0353974B2 (en) | ||
| EP0115083B1 (en) | Catalytic process for the preparation of nonionic surfactants | |
| JPH06104630B2 (en) | Method for producing alkyl group-substituted aromatic hydrocarbon | |
| EP0580263B1 (en) | Liquid concentrated aqueous solutions of salts of alkyl ether carboxylic acid, and a process for preparing such solutions | |
| CA2040834A1 (en) | Process for the preparation of alkoxylates having a narrow homolog distribution | |
| US5220077A (en) | Alkoxylation process | |
| JPH06322100A (en) | Production of low-viscosity, high-functional, light- colored polyether based on sucrose | |
| US5210323A (en) | Process for the preparation of alkoxylates having a narrow distribution of homologs using antimony pentahalide complexes as the catalyst | |
| EP0789744A1 (en) | Method of preparing non-ionic surfactants having closed end groups | |
| JPH01317546A (en) | Ethoxylation or propoxylation catalyst | |
| JP2739648B2 (en) | Alkoxylation method using lanthanum series catalyst | |
| JPH0225438A (en) | Narrow range alkanol alkoxylate | |
| JPH04334336A (en) | Method of alkoxylation catalyzed by sodium phosphate or potassium barium | |
| JPS6157694A (en) | Production of surfactant for detergent | |
| EP0361083A1 (en) | Use of metal acetyl acetonates as ethoxylation or propoxylation catalysts | |
| CA2070415A1 (en) | Alkyl polyethyleneglycol ethers as foam-suppressing additives in cleaning agents | |
| PL161488B1 (en) | Method of obtaining non-ionic surfactants |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |