Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Patent
1995-06-07
1996-06-04
Dees, Jose G.
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
526322, 560 95, 560118, 560127, 568566, C07C 69347
Patent
active
055234666
DESCRIPTION:
BRIEF SUMMARY
BACKGROUND OF THE INVENTION
The invention concerns new diacylperoxide esters, the production and use thereof.
Diacylperoxides of the general formula due to the ready formation of radicals that can trigger a polymerization. They are usually admixed with the monomers to be polymerized and develop their catalytic activity under the applied polymerization conditions. Since polymerizations are often also carried out in several steps during which intermediate products are formed that are subjected to further polymerization reactions, there is a need for polymerization catalysts which are themselves capable of polymerization and are able to copolymerize with other monomers under conditions which do not yet cause a radical decomposition of their peroxidic structures, but when they are incorporated in the polymer they form radicals under other conditions and thus facilitate a further polymerization.
Compounds which are suitable for radical formation which contain more than one group in the molecule capable of polymerization are of particular interest in this connection. The object of the invention is to provide such compounds capable of radical formation and which contain more than one olefinic double bond.
THE INVENTION
This above stated object is achieved according to the invention by diacylperoxide vinyl esters of the general formula I ##STR2## in which R denotes an alkylene residue which can be straight-chained, branched or cyclic and can contain 2 to 10 C atoms or denotes an aryl residue.
The compounds according to the invention have a good stability with half-times of about 10 hours at temperatures between about 45.degree. and 54.degree. C. and can therefore be used as comonomers for copolymerizations at temperatures of up to about 50.degree. C. without thereby substantially reducing the active oxygen (AO) content that is introduced into the copolymerisate by the compounds according to the invention. At higher temperatures, in particular above about 70.degree. C., the compounds according to the invention develop initiator activities and are particularly suitable as polymerization initiators at temperatures of 80.degree. C. and above. Phenolic compounds such as e.g. tert-butyl pyrocatechol are particularly suitable as stabilizer additives.
The production of the compounds according to the invention is carried out according to the process of the invention starting with the appropriate dicarboxylic acid semiesters. According to a first embodiment of the process according to the invention for the production of diacylperoxide vinyl esters of the general formula I, a monovinyl dicarboxylic acid of formula II ##STR3## in which R has the meaning stated for formula I, is reacted with at least equimolar amounts of dicyclohexylcarbodiimide and H.sub.2 O.sub.2 and catalytic amounts of an aromatic amine while cooling in an apolar aprotic solvent.
Toluene is preferred as the apolar aprotic solvent; other aliphatic and aromatic hydrocarbons as well as halogenated hydrocarbons also come into consideration. Dimethylaminopyridine is preferred as a catalytically active aromatic amine. Among the compounds of formula II those are preferred in which R represents an alkylene residue with 4 or 6 C atoms, a cyclohexylene residue or a phenyl residue which is substituted if desired. Substituents on the phenyl residue may be straight-chained or branched alkyl residues with 1 to 4 C atoms. Monovinyladipic acid is particularly preferred as the starting material.
The production of compounds of the general formula I can be carried out according to the process of DE-AS 1 222 4 93, either by transesterification with a vinyl ester of a lower aliphatic carboxylic acid or by reaction with acetylene in the presence of a catalyst.
According to a further embodiment of the process according to the invention for the production of compounds of the general formula I, a monovinyldicarboxylic acid chloride of formula III ##STR4## in which R has the meaning stated for formula I is reacted with an alkaline aqueous H.sub.2 O.sub.2 solution at a temperatu
REFERENCES:
patent: 3956269 (1976-05-01), Sheppard et al.
patent: 4151106 (1979-04-01), Meenen
patent: 4155937 (1979-05-01), Haas
patent: 5304609 (1994-04-01), Kohlhammer et al.
Dorn Maximilian
Hagel Eberhard
Kohlhammer Klaus
Dees Jos,e G.
Frazier Barbara S.
Peroxid Chemie GmbH
Wacker-Chemie GmbH
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