CA1081252A - Preparation of a bleach - Google Patents
Preparation of a bleachInfo
- Publication number
- CA1081252A CA1081252A CA265,400A CA265400A CA1081252A CA 1081252 A CA1081252 A CA 1081252A CA 265400 A CA265400 A CA 265400A CA 1081252 A CA1081252 A CA 1081252A
- Authority
- CA
- Canada
- Prior art keywords
- hydrogen peroxide
- peroxide
- phthalic anhydride
- diphthaloyl
- reaction
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/32—Peroxy compounds the —O—O— group being bound between two >C=O groups
- C07C409/34—Peroxy compounds the —O—O— group being bound between two >C=O groups both belonging to carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
- C07C407/003—Separation; Purification; Stabilisation; Use of additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT
The present invention provides a process for producing diphthaloyl peroxide comprising the steps of reacting particulate phthalic anhydride with aqueous hydrogen peroxide in a mobile slurry or paste and there-after separating diphthaloyl peroxide from the aqueous phase. Preferably the minimum volume of hydrogen peroxide solution is employed commensurate with obtaining a mobile slurry or paste in a mole ratio of phthalic anhydride to hydrogen peroxide of 4:3 to 1:3. Preferably the reaction is effected at a temperature of from 25 to 50°C.
Diphthaloyl peroxide is particularly suitable for washing/bleaching fabrics, optionally in conjection with an inorganic persalt e.g. sodium perborate, at a temperature of from 30 to 60°C.
The present invention provides a process for producing diphthaloyl peroxide comprising the steps of reacting particulate phthalic anhydride with aqueous hydrogen peroxide in a mobile slurry or paste and there-after separating diphthaloyl peroxide from the aqueous phase. Preferably the minimum volume of hydrogen peroxide solution is employed commensurate with obtaining a mobile slurry or paste in a mole ratio of phthalic anhydride to hydrogen peroxide of 4:3 to 1:3. Preferably the reaction is effected at a temperature of from 25 to 50°C.
Diphthaloyl peroxide is particularly suitable for washing/bleaching fabrics, optionally in conjection with an inorganic persalt e.g. sodium perborate, at a temperature of from 30 to 60°C.
Description
~ 2 S ~
The present in~ention relates to a process for the preparation of diphthaloyl peroxide.
Hitherto, it has been proposed by A. Baeyer and v. Villiger in l9Ol that diphthaloyl peroxide could be produced by reaction between phthalic anhydride and hydrog~n peroxide in dilute aqueous alkaline solution. Although Baeyer and Villiger quoted no yields, we obtained yields of only 8% of the theoretical maximum, based o~ phthalic anhydride present initially, on repetition of their work. ;
Such yields are commercially unacceptable.
According to the present invention, there is provided a process for the production of diphthaloyl peroxide comprising the steps of forming a mobile slurry or paste containing particulate phthalic anhydride and aqueous hydrogen peroxide, maintaining the slurry or paste mobile until at least some diphthaloyl peroxide has been produced, and thereafter separat~ng the diphthaloyl peroxide from the aqueous phase '` Herein, the term "mobile", used in relation to the terms "slurry" or "paste", indicates that the slurry or paste is capable of being mixed under the prevailing reaction conditions, and in the chosen apparatus.
~n general, we have found that by varying the ratio of liquid to solid in the slurry or paste, its mobility is varied, at any given set of reaction conditions in a particular item of mixing apparatus. A convenient ratio of solid to liquid, i.e. phthalic anhydride to aqueous hydrogen peroxide, is the range of 0.5 to 2.0 gm per ml, ,
The present in~ention relates to a process for the preparation of diphthaloyl peroxide.
Hitherto, it has been proposed by A. Baeyer and v. Villiger in l9Ol that diphthaloyl peroxide could be produced by reaction between phthalic anhydride and hydrog~n peroxide in dilute aqueous alkaline solution. Although Baeyer and Villiger quoted no yields, we obtained yields of only 8% of the theoretical maximum, based o~ phthalic anhydride present initially, on repetition of their work. ;
Such yields are commercially unacceptable.
According to the present invention, there is provided a process for the production of diphthaloyl peroxide comprising the steps of forming a mobile slurry or paste containing particulate phthalic anhydride and aqueous hydrogen peroxide, maintaining the slurry or paste mobile until at least some diphthaloyl peroxide has been produced, and thereafter separat~ng the diphthaloyl peroxide from the aqueous phase '` Herein, the term "mobile", used in relation to the terms "slurry" or "paste", indicates that the slurry or paste is capable of being mixed under the prevailing reaction conditions, and in the chosen apparatus.
~n general, we have found that by varying the ratio of liquid to solid in the slurry or paste, its mobility is varied, at any given set of reaction conditions in a particular item of mixing apparatus. A convenient ratio of solid to liquid, i.e. phthalic anhydride to aqueous hydrogen peroxide, is the range of 0.5 to 2.0 gm per ml, ,
- 2 -: . . ; : . . :
, ' ~
~. .. . . ~, for the initial mixture. In particular, it is highly preferable to use only enough, or only slightly more than enough liquid than the minimum to form a mobile slurry or paste. By 5electing appropriate agitators, or example, æ-blade mixers, mixtur~ c~n~ainina the minimum volume of liquid will generally be in the form of thick paste. During the course of the reaction, as the hydrogen peroxide is consumed, the mixture becomes less mobile. Mobility can be easily restored by the addition of further amounts of liquid, suitably dilute mineral acid, water or agueous hydrogen peroxide.
Preferably, the amount of liquid added is no more than the minimum amount required to restore mobility.
Alternatively, sufficient liquid may be present initially to obviate the need to add further amounts of liquid.
The amount of liquid to be added, in general, depends not only upon the extent to which the amount of liquid present initially exceeded the minimum, but also upon the mixing apparatus. The amount added often falls within the range of 0 to 1 ml per ml of liquid present initially, so that the ratio of solid to total amount of liquid is usually in the range of 0.25 to 1.5 gm per ml, more often 0.5 to 1.0 gm per ml.
The reaction to produce diphthaloyl peroxide theoret-ically requires two moles of phthalic anhydride for each mole of hydrogen peroxide. Use of excess hydrogen peroxide can be advantageous, in that it tends to reduce the amount of phthalic anhydride remaining in the finished product.
Consequently, we prefer to use a mole ratio of phthalic ~i~ 3 :. ~ . . ~ . . . . .
~, . ~ , . . .
.~ . . . . ' ! ' ' ' ' , .
anhyd~ide tv hydrogen peroxide in the range of 2:1 to 2:20 especially in the range of 2:1 to 2:5,and more particularly in the range of 2:1.5 to 2:5. A
mole ratio of more than 2 moles phthalic anhydride per mole hydrogen peroxide can be employed, but this results inevitably in the presence of phthalic anhydride in the product.
Although we wish not to be bound by any theory, it is our current belief that a substantial proportion of the phthalic anhydride remains in particulate form, and reacts with the hydrogen peroxide in the solid state. By using particles having an average particle diameter of 10~ to 50,u or lower e.g. obtained by grinding commercially available flake phthalic anhydride, the possibility of residual phthalic anhydride in the product, and thus its appearance during use of the product, can be minimised.
. _ _ .. . . .. .. .. , .. , .. _ _ . ., .. " .. , . .. _ _ . .. . .
It will be readily apparent that the mole ratio of phthalic anhydride to hydrogen peroxide is related to the ratio of solid to liquid employed initially, to the concentration of hydrogen peroxide in the solution, and to whether any additional amount of liquid added to maintain bility of the mixture contains hydrogen peroxide Thus, if the mole ratio of phthalic anhydride to hydrogen -peroxide is low, e.g. 3:2, and the ratio of solid to ;
liquid used initially is low, e.g. 0.5:1, then the -_ concentration of hydrogen peroxide is also relatively .. .... . ~
low, in the region of 10% by weight. However, the concentration is usually at least lOX, and frequently at least 20X. Thus, using a mole ratio of phthalic ~: :
~. . , . . . . , .: . .
-: . . : : . - :
5~ ~
anhydride to hydrogen peroxide from 1:1 to 2:3, and an initial solid to liquid ratio in the range of 1:1 to 1:1~5, the concentration of hydrogen peroxide falls within the range of 20 to 45% by weight. Clearly, higher mole ratios of hydrogen peroxide to phthalic anhydride require higher hydrogen peroxide concentrations or lower solids to liquid initial ratio, or addition of hydrogen peroxide during the reaction.
The reaction between phthalic anhydride and hydrogen peroxide can take place without adjustment of the pH of ~;
the system, i.e. at the pH obtained when commercially available aqueous hydrogen peroxide solution i9 contacted with the solid phthalic anhydride~ The addition of a small amount of acld e.g.a mineral acid such as sulphuric or phosphoric acid, can lead to a small increase in the reaction yield, and the addition of a small amount of alkali, e.g. an alkali metal hydroxide, such as sodium hydroxide, can tend to make the mixture more mobile.
Desirably the mixture has a pH of from 0.5 to 3 as measured, and preferably from 0.5 to 2.5. The mixture can also contain a small amount of a non-ionic surfactant, such a9 an alkyl-phenol ethoxylate e.g. trimethylnonylphenol ethoxylate, suitably in an amount o~ from 0.05% to 0.5~ by weight, based on the weight of the mixture.
In general, we have found that the mixture becomes more mobile as the temperature is raised. Consequently, : .` . -- 5 . ~
~08~ 5~
we prefer to employ a temperature of above ambient, more preferably in the range of rom 25 to 50C, thereby avoiding the increased decomposition of the product which can occur at temperatures above 50C. The reaction is normally terminated after about 5 hours or less, since a longer reaction period does not tend to significantly increase the yield of diphthaloyl pero~ide an~
can result in the formation of undesirable b~-products.
Significant yields can be obtained after reaction of at least 1 hour, conveniently up to 4 hours, especially at temperatures of about 35-40 C or higher. In one convenient method of carrying out the process, particulate phthalic anhydride and aqueous hydrogen peroxide are mixed at a pre-selected temperature in the range 25 to 50C, the temperature is maintained for a short period, such as 15 minutes, whilst sufficient liquid is added to maintain ~-~he reaction mixture mobile, and the mixture is thereafter permitted to cool to ambient temperature for the remainder of the reaction period.
,, _ . ... . . .
Suitably, the diphthaloyl peroxide can be separated from the aqueous phase by conventional techni~ues, such as by filtering or centrifuging, particularly when the volume of li~uid used in the reaction mix is significantly greater than the minimum amount required to P ~ a mobile slurry or paste. Further separation can then be effected by drying the product in conventional apparatus, such as spray driers or fluid bed driers. However, ~,, ,.. ,.. ~-~ . .... . . . . . ,, .;,,. . .:
, ,, , . : ., ~ ~. ; , : ` -. . :.
,: . .: - - . ~ ~ . . . .
: .
:
: : , .~.. ... .. , , - : , . ~ .: .
s~ ~ .
1 especially when substan~ially the minimum amount of liquid had been used in the reaction st~g~, it can be convenient to omit a filtration or centrL~uge stage, and pass directly to a spray drier or fluid bed drier. ITowever, diphthaloyl peroxide in the pure dry state is hazardous, e.g. impact sensitive, so that in practice it is h:ighly desirable to contact the damp diphthaloyl peroxide intimately with a diluent, as described in our copending Canadian patent application no. 252,390 in which a notice of allowance was issued on April 10, 1979, before drying. Such diluents can be mixed in after the reaction is completed, e.g.
magnesium sulphate. However other diluents which are substantially inert towards diphthaloyl peroxide can be present during the reaction itself. Such other diluents include fatty acids, e.g.
lauric acid, and aluminosilicates e.g. zeolites or bentonite.
Preferably, the amount of diluent or diluents used is sufficient to ~ully desensitize the product.
One of the by-products in the reaction between phthalic anhydride and hydrogen peroxide is monoperoxyphthalic acid which decomposes "in situ" more rapidly than diphthaloyl peroxide. Consequently, it is preferable to remove monoperoxy-:
phthalic acid. One way of e~fecting this, is to wash the diphthaloyl peroxide with a small amount of water and/or a non-acidic organic solvent. The organic solvent can be hydrophilic, e.g. acetone or a low molecular weight aliphatic alcohol e.g.
isopropanol, or it can be hydrophobic, e.g. a chlorinated hydro-carbon chloroform, or a liquid hydrocarbon. Washing with , :
:, ' ,~ .
.j .
GC4g 3L~i 3~L'~5~
organic solvents,Pre~erablY low molecular weight alcohols,can also remove phthalic anhydride. Con~eniently, the washlng can be effected either prior to or after separation of the product from the reaction liquor, if such separation stage is employed. One other way of removing monoperoxyphthalic acid is to employ a reducing agent e.g. sodium sulphite. This can also remove excess hydrogen peroxide, and advantageously forms, "in situ", sodium sulphate, a highly satisfactory 10 diluent. Suprisingly, sodium sulphite appears not to react marXedly with diphthaloyl peroxide, and thus the yield of the reaction remains substantially unaltered.
Preferably, diphthaloyl peroxide is treated with sufficient sodium sulphite to remove residual mono-15 peroxyphthalic acid and hydrogen peroxide, and also washed with an organic solvent as described above, in order to remove residual phthalic anhydride.
Certain embodiments according to the present invention will now be described by way of Example only.
In each Example, phthalic anhydride was added to aqueous hydrogen peroxide containing, where indicated, additives Al to A5,in a beaker held in a water bath maintained at the temperature shown, and a stirrable slurry resulted. The slurry was stirred 25 continuously with a paddle stirrer, power to the stirrer being increased after about 15 minutes when the slurry began to ~hicken rapidly. Additional amounts of aqueous hydrogen peroxide (same concentration) and/or water . '. .
.::, ., :: : : : - . :. .......... : .:: : :. .: :
, , - . , . : :: : . . . .:
were then slowly added to the slurry, over a period of about 30 minutes, restoring the slurry to approximately its original mobiliky. The slurry was then cooled to ambient for the remainder of the reaction period. In Example 10, a diluent, lauric acid, together with demineralised water was added after 1 hour of the reaction period. In Examples 11 to 16, the lauric acid together with an additional amount of water was stirred in at the end of the reaction period and mixed for 10 minutes to give a homogeneous mixture.
.. .. .. .
Diphthaloyl peroxide (DPP) was thereafter recovered by one of techniques A to E, together with an impurity monoperoxyphthalic acid (MPPA). In technique A, the slurry was filtered and water washed, both under suction, and then dried. In technique ~, the slurry was stirred with water for a minute, centrifuged and then dried. In technique C, technique A was followed, with the addition of washing with isopropanol under suction the water washed filter cake. In technique D, technigue C was followed, substituting a 20% methylated spirit in water solution for the isopropanol. In technique E, finely , ground sodium sulphite heptahydrate (90 g) together with water (40 ml) were stirred into the slurry, with cooling using an ice bath and the white cream dried 1 25 under vacuum.
In Æxamples 2 to 4 and 6 to 10, the phthalic ~:
', .
, . , i'~ `''' - 9 S~
1 ~nhydride was a commercially available flake material, and in the remaining Examples, the flake material had been ground to an average particle size of 50~. Additive Al is suf~icient aqueous sodium hydroxide to raise the pH to approximatley pH 3, A2 is 0.5 ml of 2N sulphuric acid, A3 is 3.0 ml of lN sodium hydroxide. A4 is 0.1 ml of a non-ionic surfactant, trimethyl-nonylphenol ethoxylate available commercially under the name TERGITOL * TMN, and A5 was a combination of the non-ionic sur-factant and 0.5 ml of 2N sulphuric acid.
The reaction conditions and amounts of reagents and :~
water employed are summarised in the Table, in which the mole ratio shown is that of the total amount of hydrogen peroxide to phthalic anhydride (PAn) the yield is molar, based on the amount of phthalic anhydride added, and the content by weight based on :~
the resultant dried product.
~ ~ .
~ , :
.
'.
* Trade Mark ,. ,i q.~, ~4Y
THE TABLE
Examp1e ¦Initial Amounts ~Concn. Add- Dlluent No. Amounts Added(mls) ¦ of it- Additi . - .
P~n ~tml2 ~22 ~ml) ¦ H/w2 ives ~ nt (2m0l) _ t-- . _ __ ~ . ~ , 2 30 30 0 30 35 ,.
, ' ~
~. .. . . ~, for the initial mixture. In particular, it is highly preferable to use only enough, or only slightly more than enough liquid than the minimum to form a mobile slurry or paste. By 5electing appropriate agitators, or example, æ-blade mixers, mixtur~ c~n~ainina the minimum volume of liquid will generally be in the form of thick paste. During the course of the reaction, as the hydrogen peroxide is consumed, the mixture becomes less mobile. Mobility can be easily restored by the addition of further amounts of liquid, suitably dilute mineral acid, water or agueous hydrogen peroxide.
Preferably, the amount of liquid added is no more than the minimum amount required to restore mobility.
Alternatively, sufficient liquid may be present initially to obviate the need to add further amounts of liquid.
The amount of liquid to be added, in general, depends not only upon the extent to which the amount of liquid present initially exceeded the minimum, but also upon the mixing apparatus. The amount added often falls within the range of 0 to 1 ml per ml of liquid present initially, so that the ratio of solid to total amount of liquid is usually in the range of 0.25 to 1.5 gm per ml, more often 0.5 to 1.0 gm per ml.
The reaction to produce diphthaloyl peroxide theoret-ically requires two moles of phthalic anhydride for each mole of hydrogen peroxide. Use of excess hydrogen peroxide can be advantageous, in that it tends to reduce the amount of phthalic anhydride remaining in the finished product.
Consequently, we prefer to use a mole ratio of phthalic ~i~ 3 :. ~ . . ~ . . . . .
~, . ~ , . . .
.~ . . . . ' ! ' ' ' ' , .
anhyd~ide tv hydrogen peroxide in the range of 2:1 to 2:20 especially in the range of 2:1 to 2:5,and more particularly in the range of 2:1.5 to 2:5. A
mole ratio of more than 2 moles phthalic anhydride per mole hydrogen peroxide can be employed, but this results inevitably in the presence of phthalic anhydride in the product.
Although we wish not to be bound by any theory, it is our current belief that a substantial proportion of the phthalic anhydride remains in particulate form, and reacts with the hydrogen peroxide in the solid state. By using particles having an average particle diameter of 10~ to 50,u or lower e.g. obtained by grinding commercially available flake phthalic anhydride, the possibility of residual phthalic anhydride in the product, and thus its appearance during use of the product, can be minimised.
. _ _ .. . . .. .. .. , .. , .. _ _ . ., .. " .. , . .. _ _ . .. . .
It will be readily apparent that the mole ratio of phthalic anhydride to hydrogen peroxide is related to the ratio of solid to liquid employed initially, to the concentration of hydrogen peroxide in the solution, and to whether any additional amount of liquid added to maintain bility of the mixture contains hydrogen peroxide Thus, if the mole ratio of phthalic anhydride to hydrogen -peroxide is low, e.g. 3:2, and the ratio of solid to ;
liquid used initially is low, e.g. 0.5:1, then the -_ concentration of hydrogen peroxide is also relatively .. .... . ~
low, in the region of 10% by weight. However, the concentration is usually at least lOX, and frequently at least 20X. Thus, using a mole ratio of phthalic ~: :
~. . , . . . . , .: . .
-: . . : : . - :
5~ ~
anhydride to hydrogen peroxide from 1:1 to 2:3, and an initial solid to liquid ratio in the range of 1:1 to 1:1~5, the concentration of hydrogen peroxide falls within the range of 20 to 45% by weight. Clearly, higher mole ratios of hydrogen peroxide to phthalic anhydride require higher hydrogen peroxide concentrations or lower solids to liquid initial ratio, or addition of hydrogen peroxide during the reaction.
The reaction between phthalic anhydride and hydrogen peroxide can take place without adjustment of the pH of ~;
the system, i.e. at the pH obtained when commercially available aqueous hydrogen peroxide solution i9 contacted with the solid phthalic anhydride~ The addition of a small amount of acld e.g.a mineral acid such as sulphuric or phosphoric acid, can lead to a small increase in the reaction yield, and the addition of a small amount of alkali, e.g. an alkali metal hydroxide, such as sodium hydroxide, can tend to make the mixture more mobile.
Desirably the mixture has a pH of from 0.5 to 3 as measured, and preferably from 0.5 to 2.5. The mixture can also contain a small amount of a non-ionic surfactant, such a9 an alkyl-phenol ethoxylate e.g. trimethylnonylphenol ethoxylate, suitably in an amount o~ from 0.05% to 0.5~ by weight, based on the weight of the mixture.
In general, we have found that the mixture becomes more mobile as the temperature is raised. Consequently, : .` . -- 5 . ~
~08~ 5~
we prefer to employ a temperature of above ambient, more preferably in the range of rom 25 to 50C, thereby avoiding the increased decomposition of the product which can occur at temperatures above 50C. The reaction is normally terminated after about 5 hours or less, since a longer reaction period does not tend to significantly increase the yield of diphthaloyl pero~ide an~
can result in the formation of undesirable b~-products.
Significant yields can be obtained after reaction of at least 1 hour, conveniently up to 4 hours, especially at temperatures of about 35-40 C or higher. In one convenient method of carrying out the process, particulate phthalic anhydride and aqueous hydrogen peroxide are mixed at a pre-selected temperature in the range 25 to 50C, the temperature is maintained for a short period, such as 15 minutes, whilst sufficient liquid is added to maintain ~-~he reaction mixture mobile, and the mixture is thereafter permitted to cool to ambient temperature for the remainder of the reaction period.
,, _ . ... . . .
Suitably, the diphthaloyl peroxide can be separated from the aqueous phase by conventional techni~ues, such as by filtering or centrifuging, particularly when the volume of li~uid used in the reaction mix is significantly greater than the minimum amount required to P ~ a mobile slurry or paste. Further separation can then be effected by drying the product in conventional apparatus, such as spray driers or fluid bed driers. However, ~,, ,.. ,.. ~-~ . .... . . . . . ,, .;,,. . .:
, ,, , . : ., ~ ~. ; , : ` -. . :.
,: . .: - - . ~ ~ . . . .
: .
:
: : , .~.. ... .. , , - : , . ~ .: .
s~ ~ .
1 especially when substan~ially the minimum amount of liquid had been used in the reaction st~g~, it can be convenient to omit a filtration or centrL~uge stage, and pass directly to a spray drier or fluid bed drier. ITowever, diphthaloyl peroxide in the pure dry state is hazardous, e.g. impact sensitive, so that in practice it is h:ighly desirable to contact the damp diphthaloyl peroxide intimately with a diluent, as described in our copending Canadian patent application no. 252,390 in which a notice of allowance was issued on April 10, 1979, before drying. Such diluents can be mixed in after the reaction is completed, e.g.
magnesium sulphate. However other diluents which are substantially inert towards diphthaloyl peroxide can be present during the reaction itself. Such other diluents include fatty acids, e.g.
lauric acid, and aluminosilicates e.g. zeolites or bentonite.
Preferably, the amount of diluent or diluents used is sufficient to ~ully desensitize the product.
One of the by-products in the reaction between phthalic anhydride and hydrogen peroxide is monoperoxyphthalic acid which decomposes "in situ" more rapidly than diphthaloyl peroxide. Consequently, it is preferable to remove monoperoxy-:
phthalic acid. One way of e~fecting this, is to wash the diphthaloyl peroxide with a small amount of water and/or a non-acidic organic solvent. The organic solvent can be hydrophilic, e.g. acetone or a low molecular weight aliphatic alcohol e.g.
isopropanol, or it can be hydrophobic, e.g. a chlorinated hydro-carbon chloroform, or a liquid hydrocarbon. Washing with , :
:, ' ,~ .
.j .
GC4g 3L~i 3~L'~5~
organic solvents,Pre~erablY low molecular weight alcohols,can also remove phthalic anhydride. Con~eniently, the washlng can be effected either prior to or after separation of the product from the reaction liquor, if such separation stage is employed. One other way of removing monoperoxyphthalic acid is to employ a reducing agent e.g. sodium sulphite. This can also remove excess hydrogen peroxide, and advantageously forms, "in situ", sodium sulphate, a highly satisfactory 10 diluent. Suprisingly, sodium sulphite appears not to react marXedly with diphthaloyl peroxide, and thus the yield of the reaction remains substantially unaltered.
Preferably, diphthaloyl peroxide is treated with sufficient sodium sulphite to remove residual mono-15 peroxyphthalic acid and hydrogen peroxide, and also washed with an organic solvent as described above, in order to remove residual phthalic anhydride.
Certain embodiments according to the present invention will now be described by way of Example only.
In each Example, phthalic anhydride was added to aqueous hydrogen peroxide containing, where indicated, additives Al to A5,in a beaker held in a water bath maintained at the temperature shown, and a stirrable slurry resulted. The slurry was stirred 25 continuously with a paddle stirrer, power to the stirrer being increased after about 15 minutes when the slurry began to ~hicken rapidly. Additional amounts of aqueous hydrogen peroxide (same concentration) and/or water . '. .
.::, ., :: : : : - . :. .......... : .:: : :. .: :
, , - . , . : :: : . . . .:
were then slowly added to the slurry, over a period of about 30 minutes, restoring the slurry to approximately its original mobiliky. The slurry was then cooled to ambient for the remainder of the reaction period. In Example 10, a diluent, lauric acid, together with demineralised water was added after 1 hour of the reaction period. In Examples 11 to 16, the lauric acid together with an additional amount of water was stirred in at the end of the reaction period and mixed for 10 minutes to give a homogeneous mixture.
.. .. .. .
Diphthaloyl peroxide (DPP) was thereafter recovered by one of techniques A to E, together with an impurity monoperoxyphthalic acid (MPPA). In technique A, the slurry was filtered and water washed, both under suction, and then dried. In technique ~, the slurry was stirred with water for a minute, centrifuged and then dried. In technique C, technique A was followed, with the addition of washing with isopropanol under suction the water washed filter cake. In technique D, technigue C was followed, substituting a 20% methylated spirit in water solution for the isopropanol. In technique E, finely , ground sodium sulphite heptahydrate (90 g) together with water (40 ml) were stirred into the slurry, with cooling using an ice bath and the white cream dried 1 25 under vacuum.
In Æxamples 2 to 4 and 6 to 10, the phthalic ~:
', .
, . , i'~ `''' - 9 S~
1 ~nhydride was a commercially available flake material, and in the remaining Examples, the flake material had been ground to an average particle size of 50~. Additive Al is suf~icient aqueous sodium hydroxide to raise the pH to approximatley pH 3, A2 is 0.5 ml of 2N sulphuric acid, A3 is 3.0 ml of lN sodium hydroxide. A4 is 0.1 ml of a non-ionic surfactant, trimethyl-nonylphenol ethoxylate available commercially under the name TERGITOL * TMN, and A5 was a combination of the non-ionic sur-factant and 0.5 ml of 2N sulphuric acid.
The reaction conditions and amounts of reagents and :~
water employed are summarised in the Table, in which the mole ratio shown is that of the total amount of hydrogen peroxide to phthalic anhydride (PAn) the yield is molar, based on the amount of phthalic anhydride added, and the content by weight based on :~
the resultant dried product.
~ ~ .
~ , :
.
'.
* Trade Mark ,. ,i q.~, ~4Y
THE TABLE
Examp1e ¦Initial Amounts ~Concn. Add- Dlluent No. Amounts Added(mls) ¦ of it- Additi . - .
P~n ~tml2 ~22 ~ml) ¦ H/w2 ives ~ nt (2m0l) _ t-- . _ __ ~ . ~ , 2 30 30 0 30 35 ,.
3 30 30 0 12 35
4 30 17 0 14 35 32 30 10 30 35 ;
9 32 30 10 2 35 Al 14 32 3010 5 35A4 lo 20 17 32 30 10 51~ 10 20 18 20 15 7 1212.5 fi 12 19 ~ 30 llO_ ~ 35 10 20 ',:1 .'' `', ''` , '`,' ' ' ' . .. ~ ' . ' ~
S~ ~
The Table ( cont . ) _ . __ Ex- Mole Reac- Reac~io Re- ~ield % Content %
am- Ratio tion Time cover DPP MPPA DPP MPPA
ple temp .(hot rs) Tech-No . (C ) nique _ . . _ _ _ _ l 1 1.8 25 20 B150 10 7814 2 1.8 25 5 B¦ 5711 7216 3 1.8 35-40 4 A159 7 7o10 4 1.1535-4Q 4 A¦ _ _ 6617 2.2525-30 4 C132 3 837 6 2.2525-30 4.5 B154 12 6819 7 2.25 35 4 B158 20 6826 8 2.25 40 4 A75 7 938 9 2.2525-30 4 ~44 13 6521 2.2535-40 1.67 C _ _ 421 11 2.2535-40 4 ~65 4 694 12. 2.2535-40 4 D67 3 673 13 2.2535-40 4 D30 2 513 14 2.2535 - 40 4 D74 3 743 2.2535-40 4 D71 2 702 16 2.2535-40 4 E74 2 321 17 1.2 35-40 4 D78 18 0.6 35-4Q 4 D53 4 373 , 19 2.25L 35 -40 2 D ~ 6 ~ S
., .
; _12_
9 32 30 10 2 35 Al 14 32 3010 5 35A4 lo 20 17 32 30 10 51~ 10 20 18 20 15 7 1212.5 fi 12 19 ~ 30 llO_ ~ 35 10 20 ',:1 .'' `', ''` , '`,' ' ' ' . .. ~ ' . ' ~
S~ ~
The Table ( cont . ) _ . __ Ex- Mole Reac- Reac~io Re- ~ield % Content %
am- Ratio tion Time cover DPP MPPA DPP MPPA
ple temp .(hot rs) Tech-No . (C ) nique _ . . _ _ _ _ l 1 1.8 25 20 B150 10 7814 2 1.8 25 5 B¦ 5711 7216 3 1.8 35-40 4 A159 7 7o10 4 1.1535-4Q 4 A¦ _ _ 6617 2.2525-30 4 C132 3 837 6 2.2525-30 4.5 B154 12 6819 7 2.25 35 4 B158 20 6826 8 2.25 40 4 A75 7 938 9 2.2525-30 4 ~44 13 6521 2.2535-40 1.67 C _ _ 421 11 2.2535-40 4 ~65 4 694 12. 2.2535-40 4 D67 3 673 13 2.2535-40 4 D30 2 513 14 2.2535 - 40 4 D74 3 743 2.2535-40 4 D71 2 702 16 2.2535-40 4 E74 2 321 17 1.2 35-40 4 D78 18 0.6 35-4Q 4 D53 4 373 , 19 2.25L 35 -40 2 D ~ 6 ~ S
., .
; _12_
Claims (25)
1. A process for the production of diphthaloyl peroxide comprising the steps of forming a mobile slurry or paste containing particulate phthalic anhydride and aqueous hydrogen peroxide, maintaining the slurry or paste mobile until at least some diphthaloyl peroxide has been produced, and there-after separating the diphthaloyl peroxide from the aqueuos phase.
2. A process as claimed in claim 1 wherein the initial ratio of phthalic anhydride to aqueous hydrogen peroxide is in the range of 0.5 to 2 gms per ml.
3. A process as claimed in claim 1 wherein the volume of aqueous hydrogen peroxide employed initially is substantially the minimum volume commensurate with obtaining a mobile slurry or paste, the mobility being restored to at least its original level during the course of the reaction.
4. A process as claimed in any of claims 1, 2 or 3 wherein the mole ratio of phthalic anhydride to hydrogen peroxide falls within the range of 2:1 to 1:5.
5. A process as claimed in any of claims 1, 2 or 3 wherein the mole ratio of phthalic anhydride to hydrogen peroxide falls within the range of 4:3 to 1:3.
6. A process as claimed in claim 2 wherein the mole ratio of phthalic anhydride to hydrogen peroxide falls within the range of 4:3 to 1:3 and the volume of aqueous hydrogen peroxide employed initially is substantially the minimum volume commensurate with obtaining a mobile slurry or paste, the mobility being restored to at least its original level during the course of the reaction.
7. A process as claimed in claim 1 or 3 wherein the mobility is restored by addition of an aqueous liquid.
8. A process as claimed in claim 1 or 3 wherein the mobility is restored by addition of an aqueous liquid selected from water, dilute mineral acid and hydrogen peroxide.
9. A process as claimed in claim 1 wherein the initial ratio of phthalic anhydride to aqueous hydrogen peroxide is such as to enable a mobile slurry or paste to obtain throughout the course of the reaction without addition of further amounts of liquid.
10. A process as claimed in claim 9 wherein the mole ratio of phthalic anhydride to hydrogen peroxide falls in the range of 4:3 to 1:3.
11. A process as claimed in any of claims 1, 3 or 9 wherein the concentration of hydrogen peroxide is from 10 to 45% by weight.
12. A process as claimed in any of claims 1, 3 or 9 wherein the initial pH of the aqueous hydrogen peroxide in contact with the phthalic anhydride is in the range of from pH 0.5 to 3.
13. A process as claimed in any of claims 1, 3 or 9 wherein the slurry or paste contains up to 0.5% by weight of a non-ionic surfactant.
14. A process as claimed in any of claims 1, 3 or 9 wherein the phthalic anhydride is reacted with hydrogen peroxide at a temperature of from 25 to 50°C.
15. A process as claimed in any of claims 1, 3 or 9 wherein the temperature is maintained for a short period of 25°C
15. A process as claimed in any of claims 1, 3 or 9 wherein the temperature is maintained for a short period of 25°C
Claim 15 continued to 50°C and thereafter cooled or permitted to cool to ambient temperature.
16. A process as claimed in any of claims 1, 3 or 9 wherein the phthalic anhydride is reacted with the hydrogen peroxide for 1 to 4 hours.
17. A process as claimed in Claim 6 wherein the initial pH of the aqueous hydrogen peroxide in contact with the phthalic anhydride is in the range of from pH 0.5 to 3, the concentration of hydrogen peroxide is from 10 to 45% by weight, the slurry or paste contains up to 1.5% by weight of a non-ionic surfactant, the temperature during the reaction is maintained for a short period at 35°C. to 50°C and thereafter cooled or permitted to cool to ambient temperature and the phthalic anhydride is reacted with the hydrogen peroxide for 1 to 4 hours.
18. A process as claimed in any of claims 1, 3 or 9 wherein subsequently the diphthaloyl peroxide is washed with a solvent for monoperoxyphthalic acid.
19. A process as claimed in any of claims 1, 3 or 9 wherein the diphthaloyl peroxide is subsequently washed with water and/or a low molecular weight aliphatic alcohol, each being a solvent for mono-peroxyphthalic acid.
20. A process as claimed in any of claims 1, 3 or 9 wherein the diphthaloyl peroxide is maintained in a damp condition until it is intimately contacted with a desensitising amount of a desensitising diluent.
21. A process as claimed in any of claims 1, 3 or 9 wherein a water-insoluble diluent is present during reaction between phthalic anhydride and hydrogen peroxide in an amount sufficient to desensitise the diphthaloyl peroxide formed or so added thereafter.
22. A process as claimed in any of claims 1, 3 or 9 wherein the diphthaloyl peroxide is contacted with a reducing agent capable of reacting with hydrogen peroxide and mono-peroxyphthalic acid.
23. A process as claimed in any of claims 1, 3 or wherein the diphthaloyl peroxide is contacted with sodium sulphite.
24. A process as claimed in any of claims 1, 3 or 9 wherein the diphthaloyl peroxide is maintained in a damp condition until it is intimately contacted with a desensitising amount of a desensitising diluent, the diphthaloyl peroxide is contacted with a reducing agent capable of reacting with hydrogen peroxide and monoperoxyphthalic acid and thereafter spray dried.
25. A process as claimed in claim 6, 9 and 17, wherein a water-insoluble diluent is present during reaction between phthalic anhydride and hydrogen peroxide in an amount sufficient to desensitise the diphthaloyl peroxide formed or after the reaction is added, to diphthaloyl peroxide, which has been maintained in a damp condition, in a further step, sodium sulphite or another reducing agent capable of reacting with hydrogen peroxide and monoperoxyphthalic acid is introduced and addition-ally or alternatively the diphthaloyl peroxide is washed with a solvent for monoperoxyphthalic acid and in a final step the mixture is thereafter spray dried.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB47388/75A GB1541219A (en) | 1975-11-18 | 1975-11-18 | Preparation of a dipthaloyl peroxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1081252A true CA1081252A (en) | 1980-07-08 |
Family
ID=10444790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA265,400A Expired CA1081252A (en) | 1975-11-18 | 1976-11-10 | Preparation of a bleach |
Country Status (17)
| Country | Link |
|---|---|
| JP (1) | JPS6017785B2 (en) |
| AT (1) | AT355555B (en) |
| AU (1) | AU517655B2 (en) |
| BE (1) | BE848246A (en) |
| BR (1) | BR7607682A (en) |
| CA (1) | CA1081252A (en) |
| CH (1) | CH616153A5 (en) |
| DE (1) | DE2652422C2 (en) |
| DK (1) | DK514676A (en) |
| ES (1) | ES453284A1 (en) |
| FR (1) | FR2332267A1 (en) |
| GB (1) | GB1541219A (en) |
| IT (1) | IT1069566B (en) |
| LU (1) | LU76174A1 (en) |
| NL (1) | NL7612797A (en) |
| SE (1) | SE7612862L (en) |
| ZA (1) | ZA766689B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62111076U (en) * | 1985-12-27 | 1987-07-15 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB271725A (en) * | 1926-10-26 | 1927-06-02 | Ralph Harper Mckee | Improvements in or relating to methods of making peroxides of organic acids |
| FR1528458A (en) * | 1966-06-23 | 1968-06-07 | Chefaro Mij Nv | Stabilized compositions of solid organic peroxides |
-
1975
- 1975-11-18 GB GB47388/75A patent/GB1541219A/en not_active Expired
-
1976
- 1976-11-02 AU AU19242/76A patent/AU517655B2/en not_active Expired
- 1976-11-09 ZA ZA766689A patent/ZA766689B/en unknown
- 1976-11-10 CA CA265,400A patent/CA1081252A/en not_active Expired
- 1976-11-11 LU LU76174A patent/LU76174A1/xx unknown
- 1976-11-12 ES ES453284A patent/ES453284A1/en not_active Expired
- 1976-11-12 FR FR7634405A patent/FR2332267A1/en active Granted
- 1976-11-12 BE BE1007765A patent/BE848246A/en not_active IP Right Cessation
- 1976-11-15 AT AT847776A patent/AT355555B/en not_active IP Right Cessation
- 1976-11-15 CH CH1435976A patent/CH616153A5/en not_active IP Right Cessation
- 1976-11-16 DK DK514676A patent/DK514676A/en unknown
- 1976-11-17 IT IT52225/76A patent/IT1069566B/en active
- 1976-11-17 NL NL7612797A patent/NL7612797A/en not_active Application Discontinuation
- 1976-11-17 DE DE2652422A patent/DE2652422C2/en not_active Expired
- 1976-11-17 BR BR7607682A patent/BR7607682A/en unknown
- 1976-11-17 SE SE7612862A patent/SE7612862L/en unknown
- 1976-11-18 JP JP51139025A patent/JPS6017785B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| BE848246A (en) | 1977-05-12 |
| DK514676A (en) | 1977-05-19 |
| AT355555B (en) | 1980-03-10 |
| AU517655B2 (en) | 1981-08-20 |
| IT1069566B (en) | 1985-03-25 |
| JPS5262236A (en) | 1977-05-23 |
| AU1924276A (en) | 1978-05-11 |
| CH616153A5 (en) | 1980-03-14 |
| NL7612797A (en) | 1977-05-23 |
| ES453284A1 (en) | 1977-11-01 |
| DE2652422A1 (en) | 1977-05-26 |
| FR2332267B1 (en) | 1981-09-18 |
| LU76174A1 (en) | 1977-05-18 |
| BR7607682A (en) | 1977-10-04 |
| DE2652422C2 (en) | 1985-10-03 |
| ATA847776A (en) | 1979-08-15 |
| GB1541219A (en) | 1979-02-28 |
| FR2332267A1 (en) | 1977-06-17 |
| JPS6017785B2 (en) | 1985-05-07 |
| SE7612862L (en) | 1977-05-19 |
| ZA766689B (en) | 1977-10-26 |
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