Polymerization of ethylenically unsaturated monomer employing a catalyst system comprising dialkylpyrocarbonate, organic acid anhydride, alkaline reagent and H.sub.2 O.sub.2
AssigneePPG Industries, Inc.
InventorJames A. Manner
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Abstract
Ethylenically unsaturated material susceptible to free-radical polymerization, e.g., vinyl chloride monomer, is polymerized, e.g., in an aqueous medium, with an initiator system comprising, in combination, alkaline reagent, e.g., sodium bicarbonate, organic acid anhydride, e.g., isobutyric anhydride, peroxygen compound selected from organic peroxy acid (peracid), e.g., peracetic acid, and hydrogen peroxide, and alkyl pyrocarbonate, e.g., diethyl pyrocarbonate. The initiator system is added to the polymerization medium in amounts sufficient to polymerize the ethylenically unsaturated material.
Claims28
In the process for polymerizing ethylenically unsaturated material susceptible to polymerization with free radical type initiators in an aqueous or bulk polymerization medium, the improvement which comprises conducting said polymerization in the presence of an initiator system comprising, in combination,
- a. alkaline reagent,
- b. organic acid anhydride represented by the general formula:
- ##EQU1## wherein R.sub.3 is selected from the group consisting of substituted and unsubstituted C.sub.1 - C.sub.20 alkyl, C.sub.6 - C.sub.10 cycloalkyl, and C.sub.6 - C.sub.10 aryl radicals,
- c. peroxygen compound selected from the group consisting of hydrogen peroxide and organic peroxy acid represented by the general formula:
- ##EQU2## wherein R.sub.4 is selected from the group consisting of substituted and unsubstituted C.sub.1 - C.sub.20 alkyl and C.sub.6 - C.sub.10 aryl radicals, and
- d. dialkyl pyrocarbonate represented by the general formula:
- ##EQU3## wherein R.sub.1 and R.sub.2 are each selected from the group consisting of C.sub.1 - C.sub.20 alkyl, C.sub.6 - C.sub.12 cycloalkyl, C.sub.7 - C.sub.10 aralkyl having a single aromatic ring, and C.sub.6 - C.sub.8 aryl radicals, the mole ratio of dialkyl pyrocarbonate to acid anhydride being between about 0.1:1 and about 10:1, said acid anhydride, peroxygen compound and pyrocarbonate being present in amounts sufficient to generate, in the presence of said alkaline reagent, an initiating amount of initiator and thereby polymerize the ethylenically unsaturated material.
In the process for polymerizing ethylenically unsaturated material susceptible to polymerization with free radical type initiators in an aqueous or bulk polymerization medium, the improvement which comprises conducting said polymerization in the presence of an initiator system comprising, in combination,
- a. alkaline reagent,
- b. from 0.01 to about 1 weight percent, based on ethylenically unsaturated material, of organic acid anhydride representable by the general formula:
- ##STR10## wherein R.sub.3 is selected from the group consisting of C.sub.1 - C.sub.12 alkyl radicals,
- c. hydrogen peroxide, and
- d. from 0.01 to about 1 weight percent, based on ethylenically unsaturated material, of dialkyl pyrocarbonate representable by the formula:
- ##STR11## wherein R.sub.1 and R.sub.2 are each selected from the group consisting of C.sub.1 - C.sub.12 alkyl, C.sub.6 - C.sub.10 cycloalkyl, phenyl and benzyl, the mole ratio of dialkyl pyrocarbonate to acid anhydride being between about 0.2:1 and about 1:1, the mole ratio of hydrogen peroxide to the sum of the moles of acid anhydride and dialkyl pyrocarbonate being from 0.2:1 to 2:1, thereby polymerizing the ethylenically unsaturated material.
In the process for polymerizing ethylenically unsaturated material susceptible to polymerization with free radical type initiators in an aqueous or bulk polymerization medium, the improvement which comprises conducting said polymerization in the presence of an initiator system comprising, in combination,
- a. alkaline reagent,
- b. from 0.01 to about 1 weight percent, based on ethylenically unsaturated material, of organic acid anhydride representable by the general formula:
- ##STR12## wherein R.sub.3 is selected from the group consisting of C.sub.1 - C.sub.12 alkyl radicals,
- c. organic peroxy acid representable by the general formula:
- ##STR13## wherein R.sub.4 is selected from the group consisting of C.sub.1 - C.sub.12 alkyl radicals, and
- d. from 0.01 to about 1 weight percent, based on ethylenically unsaturated material, of dialkyl pyrocarbonate representable by the general formula:
- ##STR14## wherein R.sub.1 and R.sub.2 are each selected from the group consisting of C.sub.1 - C.sub.12 alkyl radicals, C.sub.6 - C.sub.10 cycloalkyl, phenyl and benzyl, the mole ratio of dialkyl pyrocarbonate to acid anhydride being between about 0.2:1 and about 1:1, the mole ratio of peroxy acid to the sum of the moles of acid anhydride and dialkyl pyrocarbonate being from about 0.2:1 to about 10:1, thereby polymerizing the ethylenically unsaturated material.
In the process for polymerizing vinyl chloride in an aqueous or bulk polymerization medium at temperatures of between about 20.degree. and about 70.degree. C., the improvement which comprises conducting said polymerization in the presence of an initiator system comprising, in combination,
- a. alkaline buffering reagent,
- b. from 0.01 to about 1 weight percent, based on vinyl chloride, of acid anhydride selected from the group isobutyric anhydride, propionic anhydride, acetic anhydride, pivalic anhydride, and mixtures of such anhydrides,
- c. from 0.01 to about 1 weight percent, based on vinyl chloride, of dialkyl pyrocarbonate selected from dimethyl pyrocarbonate, diethyl pyrocarbonate, di-n-propyl pyrocarbonate, diisopropyl pyrocarbonate, di-n-butyl pyrocarbonate, diisobutyl pyrocarbonate, disecondarybutyl pyrocarbonate, ditertiarybutyl pyrocarbonate, di-2-ethylhexyl pyrocarbonate, dicyclohexyl pyrocarbonate, di-4-tertiarybutyl cyclohexyl pyrocarbonate, diphenyl pyrocarbonate, dibenzyl pyrocarbonate, or mixtures of such pyrocarbonates, and
- d. peroxygen compound selected from peracetic acid and hydrogen peroxide,
- the mole ratio of dialkyl pyrocarbonate to acid anhydride being between 0.2:1 and 1:1, the mole ratio of peracetic acid and hydrogen peroxide to the sum of the mole of acid anhydride and dialkyl pyrocarbonate between about 1:1 and from 0.2:1 to about 2.0:1 respectively, thereby polymerizing said vinyl chloride.
Dependencies are inferred from the claim text.