Peroxides, their preparation process and use

Details Peroxides, their preparation process and use Peroxides, their preparation process and use

2001-02-12

2002-05-07

Vollano, Jean F. (Department: 1621)

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

Organic compounds

Oxygen containing

Reexamination Certificate

active

06384287

ABSTRACT:

This is the national phase of PCT EP99/05478, filed Jul. 28, 1999, now WO 00/09478.
The present invention relates to particular peroxides, their preparation process, and their use. More particularly, the present invention relates to the preparation process of these peroxides, which are obtainable by the reaction of a corresponding ketone peroxide and an alkyl vinyl ether or an acetal. 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.
U.S. Pat. No. 3,576,826 discloses ether peroxy compounds and their preparation from alpha-substituted vinyl ether. In the class of ether peroxides (v) the adjacent peroxide groups may be separated by an unidentified aliphatic or cycloaliphatic group.
It is an object of the present invention to provide a new class of peroxides which are useful as polymerization initiators, curing agents for unsaturated polyesters, and modifying agents.
It is another object of the invention to provide peroxides with a higher reactivity in view of compounds of U.S. Pat. No. 3,576,826.
It is a further object of the invention to provide peroxides with a better storage stability at room temperature in view of compounds of U.S. Pat. No. 3,576,826.
Accordingly the present invention provides a process for the preparation of a peroxide having the general formula (I),
wherein n=1 or 2, R
1
, R
2
, R
4
, R5, and R
6
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, or R
1
and R
2
form a C
3
-C
12
cycloalkyl group, which groups may include linear or branched alkyl moieties; and each of R
1
, R
2
, R
4
, R
5
, and R
6
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
1
and R
2
may form a ring; 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, and any pair of the optionally substituted R
3
, R
4
, R
5
, and R
6
may form a ring, comprising the reaction of the corresponding ketone peroxide with the general formula (II)
wherein n, R
1
, and R
2
have the identified meaning, with an alkyl vinyl ether with the general formula (IIIa) or with an acetal with the general formula (IIIb)
wherein R
3
, R
4
, R
5
, and R
6
have the identified meaning, in the presence of a catalyst.
The ketone peroxide of formula II may be a so-called T
4
-ketone peroxide (n=1) and/or a so-called T
3
-ketone peroxide (n=2).
The T
4
-ketone peroxides having general formula IIa
which are suitable for the reaction with said alkyl vinyl ether of formula IIIa or with said acetal of formula IIIb are those formed from the following ketones: acetone, acetophenone, methyl-n-amyl ketone, ethylbutyl ketone, ethylpropyl ketone, methylisoamyl ketone, methylheptyl ketone, methylhexyl ketone, ethylamyl ketone, diethylketone, dipropyl ketone, methylethyl ketone, methylisobutyl ketone, methylisopropyl ketone, methylpropyl ketone, methyl-n-butyl ketone, methyl-t-butyl ketone, methyl cyclohexanone, isobutylheptyl ketone, diisobutyl ketone, methoxy acetone, cyclohexanone, 3,3,5-trimethyl cyclo hexanone, N-butyllevulinate, ethylacetoacetate, methylbenzyl ketone, phenylethyl ketone, methylchloromethyl ketone, methylbromomethyl ketone; also other ketones having the appropriate R
1
and R
2
groups corresponding to the peroxides of the formula II can be employed, as well as mixtures of two or more different ketones.
The T
3
-ketone peroxides having the general formula IIb
which are suitable for the reaction with said alkyl vinyl ether of formula IIIa or said acetal IIIb are those that are derived from the same group of ketones as mentioned for the T
4
-ketone peroxides.
Preferably, the ketone peroxide is formed or derived from methylethyl ketone, methylisopropyl ketone, methylisobutyl ketone, acetone, cyclohexanone and/or 3,3,5-trimethylcyclohexanone. Methyl isobutyl ketone and methyl ethyl ketone are most preferable.
The alkyl vinyl ethers of formula IIIa (in which R
4
is hydrogen) may be exemplified as follows:
vinyl 2,2-bis(vinyloxymethyl)butyl ether, allyl 2,3-epoxypropyl ether, n-propyl vinyl ether, 1-ethoxy-4-methyl-1-nonene, tert.amyl vinyl ether, 2,2-bis (4-vinyloxyphenyl)propane, hexadecyl vinyl ether, methyl vinyl ether, 4-methylhexyl vinyl ether, 2-(2-ethoxyethoxy)ethyl vinyl ether, 2-methoxyethyl vinyl ether, 2-vinyloxy ethanol, 4-methyl-1-decenyl vinyl ether, benzyl 1-methyl vinyl ether, butanediol divinyl ether, tert.butyl vinyl ether, isobutyl vinyl ether, cyclohexanedimethanol divinyl ether, cyclohexyl vinyl ether, ethyleneglycol divinyl ether, 1-ethoxy-4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexene, allyl vinyl ether, isopropyl vinyl ether, ethyl vinyl ether, tetraethyleneglycol divinyl ether, 1-methoxy-1-buten-3-yne, heptyl vinyl ether, 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone, 2-butoxyethyl vinyl ether, allyl ethyl ether, divinyl ether, 1,3-divinyloxy-2,2-dimethylpropane, 4-vinyloxybutanol, diethyleneglycol divinyl ether, 4-(vinyloxymethyl) cyclohexylmethanol, isopentyl vinyl ether, diethyleneglycol monovinyl ether, n-butyl vinyl ether, 1,4-bis(2-vinyloxyethyl)benzene, hexanediol divinyl ether, 1-methoxy-1,3-butadiene, decyl vinyl ether, 4-(allyloxymethyl)-1,3-dioxolan-2-one, 1,1-diethylpropyl vinyl ether, 2-methoxyvinyl benzene, octyl vinyl ether, bis(vinyloxy)methane, 1,4-dimethoxy-1,3-butadiene, triethyleneglycol divinyl ether, pentyl vinyl ether, octadecyl vinyl ether, triethyleneglycol methyl vinyl ether, 2,3-epoxypropyl vinyl ether, dodecyl vinyl ether, 1,1-bis(vinyloxy)butane, hexyl vinyl ether, 6-vinyloxyhexanol, (z)-1-methoxy-1-buten-3-yne, phenyl vinyl ether, 2-ethylhexyl vinyl ether, poly-THF-divinyl ether, pluriol-E-200-divinyl ether, trimethylolpropane trivinyl ether, aminopropyl vinyl ether, 2-diethylaminoethyl vinyl ether, ethyl propenyl ether.
Examples of alkyl vinyl ethers of formula IIIa in which R
4
is alkyl are as follows: 2-methoxy-2 butene, 1,1,3-trimethoxypropene, 2,3-dimethoxy-1,3-butandiene, 2-methoxypropene, 2-ethoxy propene, 2-isobutoxypropene, 2-ethoxy-2-butene, 2-isobutoxy-2-propene.
Examples of tri-substituted and cyclic alkyl vinyl ethers are 1-methoxy-2-methyl cyclohexene and 2-methoxy-2-methyl-2-butene. Examples of the cyclic alkyl vinyl ethers are 2-methyl-2,3-dihydrofuran, 2,3-dihydrofuran, 2-methyl-3,4-dihydropyran, 3,4-dihydropyran, 1-methoxy cyclohexene. Preferred are ethyl vinyl ether, isobutyl vinyl ether, propyl vinyl ether, and butyl vinyl ether. Most preferred is isobutyl vinyl ether.
Examples of acetals of formula IIb are 2,2-dimethoxypropane, 2,2-diethoxypropane (with R
4
is alkyl) or, 1,1-dimethoxybutane, 2-propyl-1,3-dioxolane, 1,1-dimethoxyethane, 1,1-diethoxyethane, 1,1-diethoxypropane, and 1,1-dimethoxycyclohexane (with R
4
is hydrogen). Preferred is 1,1-dimethoxyethane.
The reaction between the ketone peroxide of formula II and the alkyl vinyl ether of formula IIIa or acetal of formula IIIb is carried out under conditions conventional for this type of addition reaction. The temperature generally is in the range of 0-50° C. and preferably is between 1-25° C. The reaction is carried out in the presence of an acid catalyst. The amount of acid catalyst generally is 0.01-30 g/mole and preferably 0.1-15 g/mole of ketone peroxide.
The acid catalyst for the process is a conventional acidic catalyst such as a C
1
-C
10
alkane or aryl sulphonic acid, a halogenated C
1
-C
10
alkane sulphonic acid or a mixture of one or more of these compounds. The preferred catalysts for use are, but are not

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