Ketone peroxide derivatives, their preparation and use

Details Ketone peroxide derivatives, their preparation and use Ketone peroxide derivatives, their preparation and use

2000-09-05

2003-04-22

Vollano, Jean F. (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Carbonate esters

C568S563000

Reexamination Certificate

active

06552215

ABSTRACT:

The present invention relates to a preparation process for peroxides derivable from
It also relates to particular peroxides so obtainable and their use. More specifically, the present invention relates to the preparation process of peroxy esters and peroxy carbonates and mixed diperoxides, and to specific monoperoxy carbonates, diperoxy esters, diperoxy carbonates, and mixed diperoxides. Finally, the present invention relates to the use of these peroxides as polymerization initiators, curing agents for unsaturated polyesters, and modifying agents, and to formulations comprising these peroxides.
EP-A-0 043 402 discloses the production of symmetrical diperoxy esters by reacting an acid chloride with a ketone hydroperoxide in a two-phase solvent system comprising an apolar solvent. A monoperoxy ester is obtained as by-product in this reaction. If so desired, the diperoxy ester can be separated from the mixture and utilized in the pure form. A similar process is disclosed in JP-A-49-48928.
JP-A48-43491 discloses a similar method for the production of diperoxy carbonates.
Because these prior art preparation processes do not result in the formation of monoperoxy ester or monoperoxy carbonate as a major constituent, it is impossible to produce asymmetrical diperoxy esters and diperoxy carbonates and mixed peroxides in a controlled manner.
It is an object of the present invention to provide a preparation process such that the monoperoxy ester or monoperoxy carbonate is a major constituent in the reaction mixture. A major constituent is generally present in an amount of at least about 50% of the formed peroxy esters and peroxy carbonates. Preferably, the amount is above 70%, such as 80% or 90%. Generally, the amount of monoperoxy ester or monoperoxy carbonate is in the range 50%-90%, in particular 70%-90%, such as 75%-85%. Below it will be shown that the relative amount of monoperoxy ester and monoperoxy carbonate can be adjusted as desired by the selection of proper reaction constituents and reaction conditions
When the objective is to prepare symmetrical and/or asymmetrical diperoxy esters and diperoxy carbonates and mixed peroxides as well as their mixtures, these end products are formed in an amount of at least 90%, in general at least 95%, in particular at least 99%.
The present invention is based on the insight that by a proper selection of the solvents for the inert two-phase solvent system, in particular of the polar solvents, monoperoxy ester and monoperoxy carbonate are formed as a major constituent in the reaction mixture.
Accordingly, the present invention provides a process for the preparation of monoperoxy ester or monoperoxy carbonate having the general formula I:
wherein R
1
and R
2
are independently selected from the group comprising hydrogen, C
1
-C
20
alkyl, C
3
-C
20
cycloalkyl, C
6
-C
20
aryl, C
7
-C
20
aralkyl, and C
7
-C
20
alkaryl, which groups may include linear or branched alkyl moieties; and each of R
1
and R
2
may optionally be substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile, and amido, and R
3
is independently selected from the group comprising C
1
-C
20
alkyl, C
3
-C
20
cycloalkyl, C
6
-C
20
aryl, C
7
-C
20
aralkyl, and C
7
-C
20
alkaryl, which groups may include linear or branched alkyl moieties; and R
3
, may optionally be substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile, and amido, comprising the reaction of the corresponding T4-ketone peroxide with the general formula II:
wherein R
1
and R
2
have the identified meaning, with an acid halogen or halogen formate with the general formula III:
wherein R
3
has the identified meaning, in an inert two-phase solvent system comprising polar solvents.
The inert two-phase solvent system according to the present invention comprises two polar solvents. Preferably, one of the solvents is an aqueous alkali comprising-phase and the other solvent is a polar organic solvent which is not miscible with the other (aqueous) phase. A solvent is a polar solvent when its dipole moment is larger than 0D, in other words, has a certain polarity. The polarity increases proportionally with the value of the dipole moment (D). For a definition and explanation of the dipole moment reference is made to R. C. Reid, J. M. Prausnitz, B. E. Poling,
The Properties of Gases
&
Liquids
, 4th edition, 1988, ISBN 0-07-051799-1 (Ref.1) and John A. Dean,
Lange's Handbook of Chemistry
, 13th edition, 1985, ISBN 0-07-016192-5 (Ref.2).
The following Table 1 provides a listing of the dipole moments of various solvents.
TABLE 1
Dipole moments of various solvents.
Dipole moment
Dipole moment
(D)
(D)
Solvent
(Ref. 1)
(Ref. 2)
Acetonitrile
3.5
3.92
Cyclohexanone
3.1
3.01
Acetone
2.9
2.88
Acetic anhydride
3.0
2.80
Water
1.8
1.84
Butylacetate
1.8
1.86
Ethylacetate
1.9
1.81
Acetic acid
1.3
1.74
Methanol
1.7
1.70
Ethanol
1.7
1.69
n-Butanol
1.8
1.66
Dichloromethane
1.8
1.46
Dichloroethane
1.8
1.20
Diethyl ether
1.3
1.15
Chloroform
1.1
1.01
1,4-Dioxane
0.4
0
n-Butane
0
0
Methane
0
0
Methylethyl ketone (MEK)
3.3
Methylisobutyl ketone (MIBK)
2.8
Methylisopropyl ketone (MIPK)
2.8
Dimethyl ether
1.3
The polar organic solvent to be used in the process according to the invention has a dipole moment of more than 0.5D, preferably of more than 0.7D, more preferably of more than 1.0D. It is possible to change the relative amounts of monoperoxy ester and monoperoxy carbonate in the reaction mixture in view of the ketone peroxide and the acid halogen or halogen formate used by adjusting the polarity of the polar organic solvent.
In a suitable inert two-phase solvent system according to the invention, one of the solvents is an aqueous (alkali) phase and the other phase comprises as polar solvent for example alcohols, cycloalkanols, ethers, anhydrides, carbonates, alkylene glycols, amides, aldehydes, ketones, epoxides, esters, halogenated hydrocarbons such as chlorinated hydrocarbons, and mixtures thereof.
Specific examples of the above-mentioned polar solvents include, but are not limited to, diethyl ether, dimethyl ether, methylisobutyl ether, acetonitrile, ethyl acetate, methyl acetate, ethylene glycol, acetone, tetrahydrofuran, chloroform, methylene chloride, 1,2-dichloroethane, dimethyl carbonate, and the like.
By properly selecting the equivalent amount of acid halogen or halogen formate for use in the preparation process, the amounts of monoperoxy ester and monoperoxy carbonate can be adjusted further. Generally, the amount of acid halogen or halogen formate is in the range of 0.5-5 equivalents. In this case the amounts of monoperoxy ester and monoperoxy carbonate formed are at least 50% of the produced peroxides. Using 0.9-2 equivalents, the selectivity is increased further. Most preferred is an equivalent amount in the range of 0.9-1.5 equivalents. In that case the selectivity generally is above 60%, such as above 80% or even above 90%.
The proper selection of the ratio of acid halogen or halogen formate in the process also makes it possible to prepare asymmetrical peresters, percarbonates, or their mixed form by using a suitable amount of acid halogen or halogen formate in a second step to convert the remaining hydroperoxide groups. In all, one mole of the ketone peroxide (carrying two moles of hydroperoxide groups) will reacted with a total of two moles of acid halogen and/or halogen formate. By varying the amount of acylating agent in the first step and second step, the reactivity of the resulting mixture of product can be influenced. By reactivity is meant the rate at which the peroxide thermally decomposes at a certain temperature, such as conventionally determined by means of a differential scanning calorimeter (DSC) using chlorobenzene as a solvent.
Accordingly, it may be preferred to have residual T4-ketone peroxide in the final monoperester/monopercarbonate in order to make certain mixtures of peroxides, if so desired. This may be the case, for instance, wh

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