Process for the preparation of methyl p-vinylbenzoate and p-vinyl benzoic acid, and their use in latex compositions

Abstract

The present invention describes a process for the direct preparation of methyl p-vinylbenzoate from methyl p-formylbenzoate using ketene in the presence of potassium acetate. The chief products obtained from the process are about a five to two ratio of methyl p-vinylbenzoate to p-carbomethoxycinnamic acid. The latter may be thermally decarboxylated, especially in the presence of copper powder, to produce additional quantities of methyl p-vinylbenzoate. Methyl p-vinylbenzoate may further undergo hydrolysis to form p-vinyl benzoic acid. Both methyl p-vinyl benzoate and p-vinyl benzoic acid may be polymerized with ethylenically unsaturated monomers to form useful latex compositions of the present invention.

What is claimed is:  
     
         1 . A process for the preparation of methyl p-vinylbenzoate comprising reacting methyl p-formylbenzoate and ketene in the presence of a potassium salt to form methyl p-vinylbenzoate.  
     
     
         2 . The process of  claim 1  wherein the potassium salt is selected from the group consisting of potassium acetate, potassium carbonate, potassium benzoate, potassium cinnamate, and potassium proprionate.  
     
     
         3 . The process of  claim 1  wherein the molar ratio of potassium salt to methyl p-formylbenzoate is less than 0.50.  
     
     
         4 . The process of  claim 1  wherein the molar ratio of potassium salt to methyl p-formylbenzoate is less than 0.20.  
     
     
         5 . The process of  claim 1  wherein the source of ketene is selected from the group consisting of acetone, diketene, acetic anhydride, and acetic acid.  
     
     
         6 . The process of  claim 1  further comprising the addition of a solvent.  
     
     
         7 . The process of  claim 6  wherein the solvent is selected from the group consisting of aliphatic and cycloaliphatic hydrocarbons; aromatic hydrocarbons; cyclic and acyclic ethers, esters and ketones.  
     
     
         8 . A process for the preparation of p-carbomethoxycinnamic acid comprising reacting methyl p-formylbenzoate and ketene in the presence of a potassium salt to form p-carbomethoxycinnamic acid.  
     
     
         9 . The process of  claim 8  wherein the potassium salt is selected from the group consisting of potassium acetate, potassium carbonate, potassium benzoate, potassium cinnamate, and potassium proprionate.  
     
     
         10 . The process of  claim 8  wherein the molar ratio of potassium salt to methyl p-formylbenzoate is less than 0.50.  
     
     
         11 . The process of  claim 8  wherein the molar ratio of potassium salt to methyl p-formylbenzoate is less than 0.20.  
     
     
         12 . The process of  claim 8  wherein the source of ketene is selected from the group consisting of acetone, diketene, acetic anhydride, and acetic acid.  
     
     
         13 . The process of  claim 8  further comprising the addition of a solvent.  
     
     
         14 . The process of  claim 13  wherein the solvent is selected from the group consisting of aliphatic and cycloaliphatic hydrocarbons; aromatic hydrocarbons; cyclic and acyclic ethers, esters and ketones.  
     
     
         15 . A process for the preparation of methyl p-vinylbenzoate comprising thermal decarboxylation of p-carbomethoxycinnamic acid, in the presence of copper powder, to form methyl p-vinylbenzoate.  
     
     
         16 . A process for the preparation of p-vinyl benzoic acid comprising reacting methyl p-formylbenzoate and ketene, in the presence of a potassium salt, to form methyl p-vinylbenzoate; followed by hydrolysis of methyl p-vinylbenzoate to p-vinyl benzoic acid.  
     
     
         17 . The process of  claim 16  wherein the hydrolysis of methyl p-vinylbenzoate is base catalyzed.  
     
     
         18 . The process of  claim 16  wherein the hydrolysis of methyl p-vinylbenzoate is acid catalyzed.  
     
     
         19 . A latex polymer composition comprising the reaction product of methyl p-vinylbenzoate and at least one ethylenically unsaturated monomer.  
     
     
         20 . The composition of  claim 19  wherein the ethylenically unsaturated monomer is selected from the group consisting of non-acid vinyl monomers, acid vinyl monomers and/or mixtures thereof.  
     
     
         21 . The composition of  claim 20  wherein the non-acid vinyl monomer is selected from the group consisting of acetoacetoxy ethyl methacrylate, acetoacetoxy ethyl acrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethyl hexyl acrylate, isoprene, octyl acrylate, octyl methacrylate, iso-octyl acrylate, iso-octyl methacrylate, trimethyolpropyl triacrylate, styrene, a-methyl styrene, glycidyl methacrylate, carbodiimide methacrylate, C 1 -C 18  alkyl crotonates, di-n-butyl maleate, α or-β-vinyl naphthalene, dioctylmaleate, allyl methacrylate, di-allyl maleate, di-allylmalonate, methyoxybutenyl methacrylate, isobornyl methacrylate, hydroxybutenyl methacrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl ethylene carbonate, epoxy butene, 3,4-dihydroxybutene, hydroxyethyl(meth)acrylate, methacrylamide, acrylamide, butyl acrylamide, ethyl acrylamide, butadiene, vinyl ester monomers, vinyl(meth)acrylates, isopropenyl(meth)acrylate, cycloaliphaticepoxy(meth)acrylates, ethylformamide, 4-vinyl-1,3-dioxolan-2-one, 2,2-dimethyl-4 vinyl-1,3-dioxolane, and 3,4-diacetoxy-1-butene or a mixture thereof.  
     
     
         22 . The composition of  claim 20  wherein the acid vinyl monomer is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, monovinyl adipate, and mixtures thereof.  
     
     
         23 . A latex polymer composition comprising the reaction product of p-vinyl benzoic acid and at least one ethylenically unsaturated monomer.  
     
     
         24 . The composition of  claim 23  wherein the ethylenically unsaturated monomer is selected from the group consisting of non-acid vinyl monomers, acid vinyl monomers and/or mixtures thereof.  
     
     
         25 . The composition of  claim 24  wherein the non-acid vinyl monomer is selected from the group consisting of acetoacetoxy ethyl methacrylate, acetoacetoxy ethyl acrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethyl hexyl acrylate, isoprene, octyl acrylate, octyl methacrylate, iso-octyl acrylate, iso-octyl methacrylate, trimethyolpropyl triacrylate, styrene, a-methyl styrene, glycidyl methacrylate, carbodiimide methacrylate, C 1 -C 18  alkyl crotonates, di-n-butyl maleate, a or-p-vinyl naphthalene, dioctylmaleate, allyl methacrylate, di-allyl maleate, di-allylmalonate, methyoxybutenyl methacrylate, isobornyl methacrylate, hydroxybutenyl methacrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl ethylene carbonate, epoxy butene, 3,4-dihydroxybutene, hydroxyethyl(meth)acrylate, methacrylamide, acrylamide, butyl acrylamide, ethyl acrylamide, butadiene, vinyl ester monomers, vinyl(meth)acrylates, isopropenyl(meth)acrylate, cycloaliphaticepoxy(meth)acrylates, ethylformamide, 4-vinyl-1,3-dioxolan-2-one, 2,2-dimethyl4 vinyl-1,3-dioxolane, and 3,4-diacetoxy-1-butene or a mixture thereof.  
     
     
         26 . The composition of  claim 24  wherein the acid vinyl monomer is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, monovinyl adipate, and mixtures thereof.