Polymerization process and product

A process for conducting a vinyl polymerization comprising bringing together:

• a. a dispersion in an aqueous vehicle of an ionized graft polymer having a backbone including aliphatic carbon atoms on which an ionizable addition polymer side chain is bonded by a carbon-to-carbon bond in place of a hydrogen atom that is bonded thereto in the ungrafted state, said graft copolymer being formed by grafting at least one addition polymerizable monomer, including ionizable monomer, onto a polymer substrate selected from the group consisting of:
• homopolymers and copolymers of vinyl chloride;
• homopolymers and copolymers of acrylic monomers;
• hydrocarbon resins from butadiene, styrenes, and coumarone-indenes;
• polyurethanes;
• polyesters;
• and aromatic epoxy resins;
• to form at least one side chain grafted to the backbone by carbon-to-carbon bonds at one of said backbone carbons, there being ionized groups present in the dispersion, located on the side chains of the graft polymer molecules, in sufficient quantity to establish the graft polymer in suspension the aqueous vehicle, and
• b. at least one vinyl monomer and initiator therefor;
• under conditions of pressure, temperature, concentration and agitation that permit said vinyl monomer to polymerize in situ in the dispersion in dispersed form.

A process for increasing the addition polymer content of a resinous reaction product that is dispersed in an aqueous liquid vehicle wherein the said resinous reaction product comprises:

• a. an aromatic 1,2-epoxy diepoxide resin having a molecular weight above 1,000 and having a backbone including aliphatic carbons having only one or two hydrogens bonded thereto;
• b. addition polymer formed in the presence of said resin by free radical initiation polymerization of ethylenically unsaturated monomer, and
• c. graft polymer consisting of a backbone on which an ionizable addition polymer side chain is bonded by a carbon-to-carbon bond in place of a hydrogen atom that is bonded thereto in the ungrafted state, said graft polymer being formed by grafting of the addition polymer side chain to a backbone of an aromatic 1,2-epoxy diepoxide resin of the same kind as in (a) hereof, by the addition polymerization of the ethylenically unsaturated monomer in the presence of the resin;
• said addition polymer and said graft polymer being ionized, said resin providing at least 30 percent of the solids content of the initial reactants from which the said resinous reaction product is formed, and said liquid vehicle including at least one organic liquid solvent material that facilitates the processing of said resin and said polymers;
• said process comprising,
• adding addition polymerizable monomer containing ethylenic unsaturation, and initiator for the addition polymerization thereof, to the resinous reaction product in said aqueous vehicle, and
• imposing conditions of temperature, pressure, concentration and agitation thereon that cause the added monomer to polymerize in situ in the form of a dispersion of finely divided particles in said vehicle.

A process for increasing the addition polymer content of a dispersion of an acid-functional resinous reaction product in an aqueous vehicle that includes a fugitive base, wherein the said resinous reaction product comprises:

• a. an aromatic 1,2-epoxy diepoxide resin having a molecular weight above 4,000 and having a backbone chain that includes aliphatic backbone carbons having only one or two hydrogens bonded thereto;
• b. addition polymer formed in the presence of the diepoxide resin by free radical initiation polymerization of ethylenically unsaturated monomer including an acrylic acid, and
• c. graft polymer consisting of a backbone of an aromatic 1,2-epoxy diepoxide resin, of the same kind as in (a) hereof, to which backbone an ionizable addition polymer side chain is bonded by a carbon-to-carbon bond in place of a hydrogen atom that is present on an aliphatic carbon of the backbone in the ungrafted resin, said addition polymer side chain being grafted by a carbon-to-carbon bond to a said aliphatic backbone carbon atom by addition polymerization of ethylenically unsaturated monomer comprising an acrylic acid in the presence of the diepoxide resin;
• the said liquid vehicle including at least one water-miscible liquid organic solvent that facilitates processing;
• said resinous reaction product having an Acid Number on nonvolatiles in the range from about 30 to about 200, said addition polymer and said graft polymer being ionized, and the resinous reaction product being present in the aqueous vehicle as a dispersoid;
• comprising,
• adding addition polymerizable monomer containing ethylenic unsaturation, and initiator for the addition polymerization thereof, to said dispersion, and imposing conditions of temperature, pressure, concentration and agitation thereon that cause the added monomer to polymerize in situ in the form of a dispersion of finely divided particles in said vehicle.

A process comprising:

• (1) mixing together:
• (a) a dispersion in an aqueous liquid vehicle of a fugitive base and an associatively-formed resinous blend comprising:
• (i) carboxylic acid-functional graft polymer that forms at least 25% by weight of said blend,
• (ii) ungrafted carboxylic acid-functional addition polymer, and
• (iii) ungrafted aromatic 1,2-epoxy diepoxide resin;
• said graft polymer being an aromatic 1,2-epoxy diepoxide resin component having a backbone comprising aliphatic carbon atoms that have only one or two hydrogens bonded thereto in the ungrafted state, onto which backbone is grafted an addition polymer side chain component by a carbon-to-carbon bond to one of said aliphatic carbon atoms in place of one of said hydrogens, said graft polymer and said ungrafted addition polymer being acid functional and containing carboxylic acid units furnishing carboxyl groups that constitute at least about 5% of the weight of said blend;
• the ungrafted epoxy resin and the epoxy resin component of said graft polymer having an initial molecular weight above 1,000 and together constituting at least about 30% of said blend by weight;
• said acid functional polymers being ionized in the dispersion;
• (b) addition polymerizable monomer containing ethylentic unsaturation, and
• (c) initiator material for causing the monomer of (b) to polymerize;
• the proportion of the ionized blend solids of (a) to the weight quantity Q of monomer solids of (b) being from about 0.3 Q to about 20 Q;
• (2) maintaining the mixture under conditions of agitation and temperature to permit completion of the addition polymerization of the (b) monomer, with the addition polymer so formed being in the form of a dispersion of finely divided particles in said vehicle, and
• (3) recovering a dispersion of finely divided particles in said aqueous vehicle, the extent of the ionization being sufficient that the recovered product is dispersed.

A process for preparing a sprayable water-reducible composition that is suitable for formulation to a sanitary coating composition for spray application and bake-curing on the surface of a container for an edible material or beverage, by increasing the addition polymer content of a dispersion of a resinous reaction product in an aqueous vehicle that includes a basic ionizing agent that is fugitive at bake-curing temperatures, wherein the said resinous reaction product comprises:

• a. an aromatic 1,2-epoxy diepoxide resin having a molecular weight above about 4,000 and having a backbone that includes aliphatic backbone carbons having only one or two hydrogens bonded thereto;
• b. addition polymer formed in the presence of the epoxy resin by the free radical polymerization of ethylenically unsaturated monomer including an acrylic acid, and
• c. graft polymer consisting of a backbone of an aromatic 1,2-epoxy diepoxide resin, of the same kind as in (a) hereof, to which backbone an ionizable addition polymer side chain is bonded by a carbon-to-carbon bond in place of a hydrogen atom that is present on an aliphatic carbon of the backbone in the ungrafted resin, said addition polymer side chains being grafted by carbon-to-carbon bonds to at least some molecules of the epoxy resin at said aliphatic backbone carbons by the free radical addition polymerization of the ethylenically unsaturated monomer comprising an acrylic acid in the presence of the diepoxide resin, and in the presence of at least 3% by weight benzoyl peroxide based on said monomer, or equivalent free radical initiating conditions for said reaction;
• the acrylic acid being present in the monomer in sufficient quantity to impart acid functionality to the addition polymer and to the graft polymer, and to impart to said resinous reaction product an Acid Number on non-volatiles in the range from about 80 to about 90;
• said aqueous dispersion having a pH in the range from about 7 to about 9;
• the said aqueous vehicle including liquid organic solvent material that facilitates handling, water, and basic ionizing agent that ionizes the said acid-functional polymers;
• said process comprising:
• adding to said aqueous dispersion up to about 40% by weight of the total solids content of the dispersion of additional polymerizable monomer containing ethylenic unsaturation, and initiator for the addition polymerization thereof, and
• maintaining conditions of temperature, pressure, and agitation that cause the added monomer to polymerize in situ in the form of a dispersion of finely divided particles in said vehicle, the extent of the ionization being sufficient to establish and to maintain the recovered polymeric product in dispersed form.

A dispersion of finely divided film-forming synthetic polymeric solids in an aqueous vehicle for use as a coating or paint, comprising on a dry solids basis where Q is a weight quantity:

• (a) about 0.3 Q to about 20 Q of at least one ionized film forming polymer comprising a graft copolymer comprising an aromatic 1,2-epoxy diepoxide resin having a backbone including aliphatic carbon atoms having one or two hydrogens bonded thereto in the ungrafted state, and at least one side chain bonded by carbon-to-carbon grafting to one of said backbone carbons in place of one of said hydrogens, the ionization being on the side chain;
• (b) from zero up to about 20 Q of a second polymer comprising an aromatic 1,2-epoxy diepoxide resin that is not appreciably ionic in nature;
• said ionized polymer and said not appreciably ionic polymer constituting part of the dispersed phase of said dispersion, the ionization being sufficient to establish and to maintain the aforesaid polymers in dispersed form in said aqueous vehicle, and
• (c) a quantity Q of solids formed by at least one in situ addition polymerization of ethylenically unsaturated addition polymerizable monomer added to and polymerized in said aqueous dispersion in finely divided particulate form.

A composition of matter for use as a coating or paint, comprising a dispersion in an aqueous vehicle of film-forming synthetic polymeric materials, said dispersion having as a dispersed phase preformed graft polymer containing ionized units, formed from a polymer selected from the group consisting of:

• homo-polymers and copolymers of vinyl chloride;
• homopolymers and copolymers of acrylic monomers;
• hydrocarbon resins from butadiene, styrenes, and coumarone-indenes;
• polyurethanes;
• polyesters;
• and aromatic epoxy resins;
• said selected polymer having a backbone carbon chain including aliphatic carbon atoms having only one or two hydrogens bonded thereto, and said graft polymer being formed by having at least one side chain grafted to the backbone carbon chain by a carbon-to-carbon bond in place of one of said hydrogens, wherein the ionized units are located on the side chain, and an in situ polymerized ethylenically unsaturated monomer, in the form of a dispersion of finely divided particles in said vehicle, the ionization being sufficient to establish and to maintain the aforesaid polymers in dispersed form in said aqueous vehicle.

A composition of matter for use as a coating of paint, comprising a liquid aqueous vehicle containing therein an ionizing agent and a pre-formed graft polymer having an aromatic 1,2-epoxy diepoxide resin backbone, the epoxy resin having an epoxy equivalent weight of at least 500 in its ungrafted state and having aliphatic backbone carbon chains including aliphatic carbon atoms having only one or two hydrogens bonded thereto, to which backbone at least one side chain is bonded by carbon-to-carbon grafting to an aliphatic backbone carbon of the epoxy resin in place of one of said hydrogens, whereby the graft polymer is resistant to hydrolysis at the grafting site, the side chain comprising polymerized ethylenically unsaturated monomer units furnishing ionizable sites, the composition also comprising preformed addition polymerized ethylenically unsaturated monomer associatively formed with said graft polymer by addition polymerization of ethylenically unsaturated monomer in the presence of the epoxy resin, and in the presence of at least 3% by weight benzoyl peroxide based on said monomer, or equivalent free radical initiating conditions for said reaction, said liquid vehicle comprising a mixture of water and of at least one water-miscible organic solvent liquid, and an in situ polymerized ethylenically unsaturated monomer, all of said polymers being synthetic film-forming polymers, the ionization being sufficient to establish and to maintain the aforesaid polymers in dispersed form in said aqueous vehicle.

A water-reducible composition for use as a coating or paint, comprising in situ polymerized ethylenically unsaturated monomer in a dispersion of a resinous reaction product in an aqueous vehicle, wherein the resinous reaction product comprises:

• a. an aromatic 1,2-epoxy diepoxide resin having an epoxy equivalent weight above about 2,000 and having a backbone chain that includes aliphatic backbone carbon atoms having only one or two hydrogen atoms bonded thereto;
• b. addition polymer formed in the presence of the diepoxide resin by addition polymerization of ethylenically unsaturated monomer including an acrylic acid;
• and
• c. graft polymer consisting of a backbone of an aromatic 1,2-epoxy diepoxide resin, of the same kind as in (a) hereof, to which backbone an ionizable addition polymer side chain is bonded by a carbon-to-carbon bond in place of a hydrogen atom that is present on an aliphatic carbon of the backbone in the ungrafted resin, said addition polymer side chain being grafted by a carbon-to-carbon bond to a said aliphatic backbone carbon by free radical initiated addition polymerization of ethylenically unsaturated monomer comprising an acrylic acid in the presence of the diepoxide resin, and in the presence of at least 3% by weight benzoyl peroxide based on said monomer, or equivalent free radical initiating conditions for said reaction, the acrylic acid being present in the monomer in sufficient quantity to impart acid functionality to the addition polymer and to the graft polymer, and to impart to the resinous reaction product an Acid Number on non-volatiles in the range from about 40 to about 150;
• said aqueous vehicle including at least one water-miscible organic solvent liquid in which the said diepoxide resin is soluble,
• said composition having a pH in the range from about 7 to about 9,
• the in situ polymerized monomer providing up to about 40% by weight of the total solids content of the composition, all of said polymers being synthetic film-forming polymers, and
• said aqueous vehicle including a fugitive base, that ionizes the acid-functional polymers, the ionization being sufficient to establish and to maintain the aforesaid polymers in dispersed form in said aqueous vehicle.

A sprayable, water-reducible composition suitable for use in the formulation of sanitary coatings comprising an in situ polymerized ethylentically unsaturated monomer in a dispersion of a film-forming resinous reaction product in an aqueous vehicle, the sprayable composition having said aqueous vehicle as a continuous phase and finely divided film-forming synthetic polymer solids, including said resinous reaction product, dispersed in the aqueous vehicle as a discontinuous phase, the sprayable composition comprising, on a 100% total weight basis:

• a. from about 10% to about 30% of said finely divided solids forming a continuous phase, and
• b. the balance up to 100% thereof being the aqueous vehicle;
• c. the finely divided solids comprising, on a 100% total non-volatile solids basis:
• i. from about 5% to about 40% by weight of in situ polymerized ethylenically unsaturated monomers, and
• ii. the balance up to 100 weight percent thereof being provided by said resinous reaction product that in turn comprises,
• (1) an aromatic 1,2-epoxy diepoxide resin having an epoxy equivalent weight not substantially below about 2,000 and having a backbone chain that includes aliphatic backbone carbon atoms having only one or two hydrogens bonded thereto;
• (2) addition polymer formed by the addition polymerization of ethylenically unsaturated monomer that furnishes ionizable sites in the addition polymer, and
• (3) graft polymer consisting of a backbone of an aromatic 1,2-epoxy diepoxide resin, of the same kind as in (1) hereof, to which backbone an ionizable addition polymer side chain is bonded by a carbon-to-carbon bond in place of a hydrogen atom that is present on an aliphatic carbon of the backbone in the ungrafted resin, said addition polymer side chain being grafted by a carbon-to-carbon bond to a said aliphatic backbone carbon of the diepoxide resin by free radical initiated addition polymerization of ethylenically unsaturated monomer in the presence of the epoxy resin and in the presence of at least 3% by weight benzoyl peroxide based on said monomer, or equivalent free radical initiating conditions for said reaction;
• said addition polymer and said graft polymer having ionizable sites, the ionizable sites of the graft polymer being located in its side chains;
• the said aqueous vehicle including water, at least one water-miscible organic solvent, and a fugitive ionizing agent, the said polymers being ionized in said vehicle by said ionizing agent, the extent of ionization being sufficient to establish and to maintain the solids dispersed in the aqueous vehicle in finely divided particulate form.