MXPA99008640A - Compositions of acrylic polymers, with crystalline lateral chains, and processes for preparation - Google Patents

Abstract

Acrylic polymer compositions with crystalline side chains are disclosed. Also disclosed are processes for solution polymerization, aqueous suspension polymerization and aqueous dispersion polymerization for the preparation of acrylic polymer compositions with crystalline side chains. Also disclosed are methods of use for acrylic polymer compositions with crystalline side chains, including dry powder coatings, wax replacements in floor polishes and wood coatings, coatings of nonwovens and textiles, adhesives, and hot melt adhesives

Description

COMPOSITIONS OF ACRYLIC POLYMERS. WITH CRYSTAL SIDE CHAINS. AND PROCESSES FOR YOUR PREPARATION Acrylic polymers have many useful properties, such as durability, flexibility in composition and glass transition temperatures ("Tg"), weather resistance, adhesion to polar substrates and compatibility with many polar polymers and inorganic components. While each of the properties may be convenient, it is difficult to obtain all of them in a polymer. Often it is necessary to sacrifice one property to gain another, because the properties of the polymer depend on the composition of this polymer, molecular weight and Tg. For example, a low Tg may be desirable for a polymer composition which would be useful in adhesive applications, but the low Tg polymer can not provide good durability. In addition, because acrylic polymers are generally amorphous, they are not effective in all applications where crystallinity is desired. They do not adhere well to most non-polar substrates, such as polyolefins. Amorphous acrylic polymers are also inferior in terms of water resistance and durability, compared to polyolefins. Therefore, there is a need for low cost polymer compositions, which provide durability, flexibility in composition and Tg, weather resistance, adhesion to polar and non-polar substrates, compatibility with polar polymers and inorganic components, and waterproof. Prior methods for achieving a combination of the desired properties of the acrylic polymers and the olefin polymers in "a single" polymer include physically mixing an acrylic polymer and an olefin polymer or copolymerizing an olefinic monomer and an acrylic monomer. These methods have not been successful. The physical mixture of acrylic polymers and polyolefins do not usually produce useful compositions, because the two polymers are incompatible. The copolymerization of an olefin monomer and an acrylic monomer is difficult, because there is poor reactivity between the two monomers. In addition, the copolymerization of the two monomers usually results in a composition with an average of the combined properties of each homopolymer, rather than improved properties. U.S. Patent No. 5,387,450 ('450) attempts to solve the problem. This patent discloses polymer compositions containing, as polymerized units, crystallizable side chain monomers, and are useful as adhesives. Below the melting temperature of the crystallizable side chain, the polymer is not sticky. Above the melting temperature of the crystallizable side chain, the polymer returns to a sticky adhesive. The compositions are required to contain at least 50 weight percent of a crystallizable side chain monomer. The crystallizable side chain monomers are acrylates or methacrylates with 14 to 22 carbon atoms as the side chains. Although this patent provides a route to achieve some of the properties discussed above, there are still several problems to be solved by the patent. The crystallizable side chain monomers of the patent have lower melting points and are more soluble in organic solvents than the crystallizable side chain monomers are more carbon atoms in the side chains. Therefore, a problem is that the patent does not teach how to process crystallizable side chain monomers with more carbon atoms in the side chains, which require higher melting temperatures and are less soluble in organic solvents. Another problem is that the crystallizable side chain monomers are relatively new and, due to their special structure, are estimated to cost several times more than the other monomeric components. For these reasonsIt is convenient to minimize the amount of crystalline side chain monomer in a polymer and still achieve the properties described above. Despite the exposure of the '450 patent, there is still a need for low cost polymer compositions, which provide durability, flexibility in composition and Tg, weather resistance, adhesion to polar and non-polar substrates, compatibility with polar polymers and inorganic components and water resistance. To provide the desired polymer compositions, the inventors have prepared polymers containing an acrylic backbone with less than 50 weight percent of a synthetic wax monomer ("S M"). This SWM contains crystalline polyethylene side chains and, therefore, is a crystallizable side chain monomer. A benefit of the copolymers of this invention is that physical entanglement can be achieved through the association of a polymer component. This association can be crystallization or simply phase separation. The physical entanglements that are formed are not permanent and can be "deinterlaced" by heating. Through such physical entanglement, the skeletal polymer matrix forms a network-like structure, yet can be completely de-interleaved when the polymer is heated above the melting temperature of the association blocks. The formation of a network structure helps to prevent the loss of physical properties when the molecular weight or Tg of the backbone polymer has to be reduced for process or flexibility reasons. In a first aspect, the present invention supplies a polymer that includes as polymerized units: A) from 1 to less than 50 weight percent of a synthetic wax monomer of the formula I: where Ri is selected from H and CH3, R2 is selected from H and Ci-C5 alkyl, R3 is selected from H and CH3, n = 9-115, preferably 12-90, more preferably 15-50 and m = 0-1370, preferably 0-65, more preferably 0-50; and B) from 50 to 99 weight percent of at least one second monomer. Previously, it had been difficult to prepare the polymer compositions described above. For example, the '450 patent, described above, used a solution polymerization reaction of one operation to polymerize the monomers. For a process in solution, it is convenient to be able to gradually add the SWM to the polymerization basin, because it is believed that the SWM will be incorporated more uniformly in the polymer. The emulsion and suspension processes are convenient because they allow a reduction or elimination of organic solvents. The '450 patent does not address this. Consequently, there is a continuing need for processes to prepare polymers containing the SWM. The inventors have supplied several approaches in the preparation of polymer containing the SWM. In an approach, an aqueous slurry of SWM is prepared prior to the polymerization of the SWM. This aqueous paste can be used to prepare polymers in solution or suspension. For a solution process, the aqueous paste can be combined with additional monomers or organic solvents and co-fed to the reactor with an initiator. For a suspension process, the aqueous paste is combined with an initiator and an aqueous and polymerized solution. In a second aspect, the present invention provides a method for preparing an aqueous paste polymer by: 1) forming an aqueous paste by cooling a solution containing a synthetic wax monomer and a solvent; 2) forming a reaction mixture by mixing at least one second monomer with the aqueous paste; and 3) polymerizing the reaction mixture in the presence of an initiator. In a third aspect, the present invention provides a method for preparing a polymer of an emulsion, by dissolving a synthetic wax monomer in at least one second monomer, to form a solution, mixing water and at least one surfactant, to supply a second solution, form an emulsion of monomers, mixing the first and second solutions, provide a reactor with hot water and polymerize the emulsion of monomers, adding this emulsion of monomer and at least one initiator to the reactor. In a fourth aspect, the present invention provides a method of coating, which includes applying a composition containing the polymer of the invention to a substrate. As used throughout this specification, the term (meth) acrylic acid is understood to mean both acrylic and methacrylic acid. Similarly, as used in this specification, the term (meth) acrylate is understood to mean the esters of both acrylate and methacrylate. The synthetic wax monomers (SWM) of this invention are monomers of (meth) acrylate, ethylenically unsaturated, C24 to Cao, preferably C50 to C50, or their ethoxylates, and are formed from alcohols of synthetic C24 to CaO waxes. SWM are formed by the reaction of a C24 to C8o synthetic wax alcohol or its ethoxylate, with an alkyl (meth) acrylate, in the presence of a zirconium catalyst and a suitable inhibitor, although they can be obtained by other well processes. known in art. Suitable alcohols or ethoxylates are available from Baker Petrolite, Inc., Houston, Texas, as Unilin ™ or Unithox ™ products. Suitable examples of the SWM include the acrylate or methacrylate esters of Unilin 350, Unilin 450, Unilin 550, Unilin 700 and Unithox 450. The amount of the SWM in the polymer is typically from 1% to less than 50%, preferably from 3%. to 45%, more preferably from 4 to 40%, and especially preferred from 5 to 35% by weight, based on the total weight of the polymer of this invention.

This at least one second monomer can be an ethylenically unsaturated monomer. Suitable ethylenically unsaturated monomers include acrylic and methacrylic acid and their esters. Generally, the (meth) acrylates are the Ci (meth) acrylates up to C2. The (meth) acrylate is 50 to 99%, preferably 55 to 97%, more preferably 60 to 96% by weight, based on the total weight of the polymer of the composition of this invention. Examples of the alkyl (meth) acrylate are methyl methacrylate (MMA), ethyl methacrylate (EMA), methyl and ethyl acrylate, propyl methacrylate, butyl methacrylate (BMA) and butyl acrylate (BA), methacrylate isobutyl (IBMA), hexyl and cyclohexyl methacrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate (EHA), 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, isodecyl methacrylate (IDMA, based on the mixture of branched alkyl isomer (Cio) / undecyl methacrylate, dodecyl methacrylate (also known as lauryl methacrylate), tridecyl methacrylate, tetradecyl methacrylate (also known as myristyl methacrylate), pentadecyl methacrylate, dodecyl-pentadecyl methacrylate (DPMA), a mixture of linear and branched isomers of methacrylates of dodecyl, tridecyl, tetradecyl and pentadecyl, and lauryl-myristyl methacrylate (LMA), a mixture of methacrylates of dodecyl and tetradecyl cyl, hexadecyl methacrylate, heptadecyl methacrylate, octadecyl methacrylate, nonadecyl methacrylate, cosyl methacrylate, icosyl methacrylate, cetyl-icosyl methacrylate (CDEMA), a mixture of hexadecyl, octadecyl, cosyl and icosyl methacrylates; and cetyl-stearyl methacrylate (SMA), and a mixture of hexadecyl and octadecyl methacrylates. Mixtures of one or more (meth) acrylate can also be used. Another class of suitable ethylenically unsaturated monomers, useful as this at least one second monomer, are the vinyl aromatic monomers, which include, among others, styrene, a-methylstyrene, vinyltoluene, p-methylstyrene, ethylvinylbenzene, vinyl. -naphthalene, vinylxylenes, and the like. The vinylaromatic monomers may also include their corresponding substituted counterparts, such as the halogenated derivatives, ie they contain one or more halogen groups, such as fluorine, chlorine or bromine; and derivatives of nitro, cyano, alkoxy, haloalkyl, carbalkoxy, carboxy, mino, alkylamino, and the like. The vinylaromatic monomers can be used at levels of 0 to 50%, preferably 0 to 30% by weight, based on the total weight of the polymer of the composition of this invention. Another class of suitable ethylenically unsaturated monomers, which can be used like this at least one second monomer, are the nitrogen-containing ring compounds, and their thio-analogues, such as vinylpyridines, such as 2-vinylpyridine or 4-viniñiridine, and the C-vinyl pyridines substituted with lower alkyl (C? -8), such as: 2-methyl-5-vinyl-pyridine, 2-ethyl-5-vinylpyridine, 3-methyl-5-vinylpyridine, 2, 3 -dimethyl-5-vinyl-pyridine, 2-methyl-3-ethyl-5-vinylpyridine; quinolines and isoquinolines substituted by methyl, N-vinylcaprolactam, N-vinylbutyrolactam, N-vinylpyrrolidone, vinyl imidazole, N-vinyl carbazole, N-vinyl succinimide, acrylonitrile, o-, m-, or p-aminostyrene, maleimide, N- vinyl-oxazolidine, N, N-dimethyl-aminoethyl-vinyl-ether, ethyl-2-cyano-acrylate, vinyl-acrylonitrile, N-vinylphthalimide. Also included are N-vinyl-thio-pyrrolidone, 3-methyl-1-vinyl-pyrrolidone, 4-methyl-1-vinyl-pyrrolidone, 5-methyl-1-vinyl-pyrrolidone, 3-ethyl-1-vinyl- pyrrolidone, 3-butyl-1-vinyl-pyrrolidone, 3,3-dimethyl-1-vinyl-pyrrolidone, 4,5-dimethyl-1-vinynyl pyrrolidone, 5,5-dimethyl-1-vinyl-pyrrolidone, 3, 3,5-trimethyl-1-vinyl-pyrrolidone, 4-ethyl-1-vinyl-pyrrolidone, 5-methyl-5-ethyl-1-vinylpyrrolidone, 3,4,5-trimethyl-1-vinyl-pyrrolidone, and others N-vinyl-pyrrolidones substituted with lower alkyl. Nitrogen-containing ring compounds and thio-analogs can be used at levels of 0 to 50%, preferably from 0 to 30% by weight, based on the total weight of the polymer of the composition of this invention. Another class of suitable ethylenically unsaturated monomers, which may be useful as this at least one second monomer, are the substituted ethylene monomers, such as vinyl acetate, vinyl chloride, vinyl fluoride, vinyl bromide, vinylidene chloride, vinylidene fluoride, vinylidene bromide, acrylonitrile, methacrylonitrile, acrylic acid (AA), and their corresponding amides and esters, methacrylic acid (MAA) and its corresponding amides and esters. The substituted ethylene monomers may be used at levels of 0 to 50%, preferably 0 to 30% by weight, based on the total weight of the polymer of the composition of this invention. Another class of acrylic and methacrylic acid derivatives which may be useful as this at least one second monomer are represented by the substituted alkyl acrylates and methacrylates and the substituted acrylamide and methacrylamide monomers. Examples include the (meth) acrylates wherein the alkyl group is substituted with halogen, such as fluorine, chlorine or bromine; and the nitro, cyano, alkoxy, haloalkyl, carbalkoxy, carboxy, amino, alkylamino, glycidyl (meth) acrylate derivatives and the like. The substituted alkyl acrylate and methacrylate and the substituted acrylamide and methacrylamide monomers can be used at levels of 0 to 50%, preferably 0 to 30% by weight, based on the total weight of the polymer of the composition of this invention . Each of the substituted monomers, which may be useful as this at least one second monomer, may be a single monomer or a mixture of monomers having different numbers of carbon atoms in the alkyl moiety. This alkyl portion of each monomer can be linear or branched.

The hydroxyalkyl (meth) acrylate monomers may also be useful in this invention as this at least one second monomer. Among the methacrylate and hydroxyalkyl acrylate monomers suitable for use in the present invention are 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl methacrylate, methacrylate 1- methyl-2-hydroxyethyl, 2-hydroxy-propyl acrylate, 1-methyl-2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate and 2-hydroxybutyl acrylate. The hydroxyalkyl (meth) acrylate monomer can be used at levels of 0 to 50%, preferably 0 to 30% by weight, based on the total weight of the polymer of the composition of this invention. Further examples of substituted (meth) acrylate monomers, useful as this at least a second monomer, are those alkyl acrylate and methacrylate monomers with a dialkylamino group on the alkyl radical, such as dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, and similar. Other examples of substituted (meth) acrylate monomers, useful as this at least a second monomer are the nitrogen-containing ring compounds (previously described) and the methacrylamide and dialkylaminoalkyl acrylamide monomers, such as the methacrylamide of N, N- dimethylaminoethyl, N, N-dimethyl-aminopropyl methacrylamide, N, N-dimethylaminobutyl methacrylamide, N, N-di-ethylaminoethyl methacrylamide, N, N-diethylaminopropyl methacrylamide, N, N-diethylaminobutyl methacrylamide, N- (1 , l-dimethylyl-3-ooobutyl) acrylamide, N- (1,3-diphenyl-1-ethyl-3-oxybutyl) acrylamide, N- (1-methyl-1-phenyl-3-oxobutyl) methacrylamide and 2-hydroxyethyl acrylamide, N-methylacrylamide aminoethyl ethylene urea, N-methacryloxyethylmorpholine, N-maleimide dimethylaminorpopilamine, and the like. The monomers of ethylenically unsaturated acids, such as, for example, acrylic acid, methacrylic acid, crotonic acid, phosphoethyl methacrylate, 2-acrylamido-2-methyl-1-propanesulfonic acid, sodium vinyl sulfonate, itaconic acid, fumaric acid , maleic acid, monomethyl itaconate, monomethyl fumarate, monobutyl fumarate and maleic anhydride, at least one second monomer may also be used as the latter in the polymers of this invention. The ethylenically unsaturated acid monomers can be used from 0 to 20% by weight, based on the weight of the polymer. The polymer of this invention can be linear, branched or partially entangled. It can be interlaced later. By interlacing later it is meant that the polymer can have reactive groups that do not react during the polymerization, but can react after the polymerization to provide the entanglement. The physical form of the polymer can be pellets, globules, emulsion, solution or pieces. The polymer can have a molecular weight of 5,000 to 5,000,000, preferably 10,000 to 2,000,000, more preferably 20,000 to 1,000,000, as determined by gel permeation chromatography ("GPC"). The polymer can have a melting point of 20 to 110 ° C, as determined by differential scanning calorimetry ("DSC"). Alternative processes can be used to prepare the polymer of this invention. Suitable processes include solution polymerization, aqueous suspension polymerization and aqueous dispersion polymerization (both batch and semi-continuous).

In the aqueous slurry process of the invention, an aqueous slurry is formed by cooling a solution containing the SWM and a solvent, until this SWM precipitates out of the solution as crystals. This process can be used for polymerization in solution or in suspension. For a solution process mode, the SWM can be mixed with an organic solvent and heated until this SWM melts and dissolves, and then cooled, with stirring. Suitable solvents include, but are not limited to, hexane, heptane, xylene, toluene, ethyl acetate, butyl acetate, hexanol, heptanol, octanol, decane, decalin, and the like. After cooling, other monomers can be added. Suitable monomers include acid (meth) acrylic, esters of (meth) acrylic acid, (meth) acrylic amides, aromatic vinyl monomers, substituted ethylene monomers, functional monomers with a rear crosslinking group, multifunctional monomers, and mixtures thereof. The cooled aqueous paste can be gradually added to the reaction vessel in the presence of an initiator to form polymers in solution. For the suspension process mode, the SWM can be mixed with other monomers and an aqueous solution and heated until the SWM melts and dissolves in the organic phase. The mixture is cooled below the temperature at which the polymerization will begin and then the initiator is added. The mixture is stirred to uniformly incorporate the initiator into the organic phase. The cooled mixture containing the initiator is then heated and the stirring rate is increased to form a dispersion and initiate the polymerization. The aqueous solution may contain a suspending / dispersing agent to stabilize the polymerization droplets. This suspending / dispersing agent can be used at 0.01 to 5% by weight, based on the total weight of the mixture. Suitable suspending / dispersing agents include polyalkyldimethylammonium chloride, polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose or various other cellulose materials, polyvinyl pyrrolidone, natural gum, powdered dispersants and the sodium allyl of the homopolymer or copolymers of poly ( met) acrylic. In the dispersion process of the invention, a solution, containing the SWM, in at least one second monomer, is provided. In the process, the solution can be obtained by heating a mixture of SWM in at least one second monomer, until the synthetic wax monomer melts and dissolves, as described above. The solution can be mixed with a second aqueous solution of the surfactant, to create an emulsion of monomers. In one embodiment of the dispersion process, this at least one second monomer of the first solution can be selected from the monomers described above, which include (meth) acrylic acid, (meth) acrylic acid ethers, (meth) acrylic amides , vinyl aromatic monomers, substituted ethylene monomers, functional monomers with a subsequently crosslinkable group, multifunctional monomers, and mixtures thereof. In a second embodiment of the dispersion process, this at least one second monomer of the first solution can be selected from an SWM containing polyethylene blocks. In this case, the second SWM acts as an aqueous dispersant for the first SWM. These (Unithox ™ 450 acrylate), may be suitable for these purposes. Similar, low molecular weight, two-block polymers, without the polymerizable (meth) acrylate end group, such as poly (ethylene) -b-poly (ethylene oxide) -OH (Unithox ™ ethoxylate) can also be used as dispersants. The dispersants can be used from 0 to 20% by weight, preferably from 1 to 15% by weight, more preferably from 2 to 10%, based on the total weight of the first synthetic wax monomer. For both embodiments of the dispersion process, the second solution may be an aqueous solution of the surfactant. The surfactants can be used from 0.1 to 5% by weight, based on the total weight of the monomer mixture. The surfactants can be anionic, nonionic or cationic. Anionic surfactants or a combination of an anionic surfactant with a nonionic surfactant are preferred. In the processes of the invention, a reaction mixture is formed by mixing at least one second monomer with the SWM. The amount of this at least one second monomer mixed with the SWM ranges from 50 to 99%, preferably from 60 to 97%, more preferably from 65 to 95% by weight, based on the weight of the SWM. This at least one second monomer to be mixed with the synthetic wax monomer can be selected from the monomers described above, which include (meth) acrylic acid, esters of (meth) acrylic acid, (meth) acrylic amides, vinyl aromatic monomers, substituted ethylene monomers, functional monomers with a subsequently crosslinkable group, multifunctional monomers, and mixtures thereof. In the processes of the invention, the monomers can be polymerized by co-feeding the reaction mixture and an initiator into a reactor or batch-polymerizing a reaction mixture in a reactor, a temperature sufficient to initiate the polymerization. Typically, the reactor is at a temperature of 75 to 110 ° C. The initiator is preferably insoluble in water and can be selected from peroxyesters, dialkyl peroxides, alkylhydroperoxides, persulfates, azo initiators, redox initiators and other known free radical initiators. Part of the initiator is incorporated into the polymer as end groups. The amount of the initiator used is generally 0.05 to 5% by weight, based on the weight of the total monomer. The dispersion process will supply a latex polymer. The latex polymer can be isolated by any method known in the art, such as spray drying, freeze drying, or coagulation. The suspension process will supply polymer globules. These polymer globules can be isolated by filtration. The solution process will provide a homogenous polymer solution when a good solvent is used. Toluene, xylene and decalin are examples of good solvents. If one wishes to isolate the polymer from the solution, one will use a poor solvent. By poor solvent it is understood that the polymer is soluble in the solvent at high temperature, but insoluble at low temperature. Examples of poor solvents are heptane, hexane or other saturated alkane solvents. The polymer can be isolated by cooling the solution followed by filtration. When a solid is isolated, this solid can contain the solvent and can be vacuum dried at room temperature to give net pieces of polymer. The crumbly solid can also be diluted in the solvent, reheated to form a solution, cooled with stirring, filtered by vacuum, and air dried in a Buchner funnel to deliver solid pieces of polymer. Chain transfer agents can be used to regulate the molecular weight in the processes for preparing the polymers of this invention. Suitable chain transfer agents include organic thiol compounds, such as n-odedecyl-mercaptan and the like. The chain transfer agent can be used in 0 to 10% by weight of the total monomer mixture. When used in the processes for preparing the polymers of the invention, part of the structure of the chain transfer agent is incorporated into the polymer as an end group. A salt may be used in the suspension processes of preparing the polymers of this invention to reduce the solubility of the organic monomers in the aqueous phase. This salt can be used from 0 to 8% by weight, based on the total weight of the mixture. Suitable salts include sodium chloride, potassium chloride and the like. Organic solvents may be used in the suspension process to prepare the polymers of this invention to improve the solubility of synthetic wax (meth) acrylate in the other monomers. The organic solvents can be used at 0 to 200% by weight, preferably 0 to 100% by weight, based on the total weight of the synthetic wax (meth) acrylate.

A regulator may be useful in dispersion processes to prepare the polymers of this invention, to maintain the pH of the aqueous phase. Suitable regulators include the sodium, potassium and ammonium salts of carbonate, bicarbonate, acetate, phosphate and borate. These regulators can be used from 0 to 5%, based on the total weight of the composition. Sodium nitrite or sodium perborate may be useful as the radical inhibitors in dispersion processes, to prepare the polymers of this invention, to inhibit any unwanted polymerization in the aqueous phase. The radical inhibitors can be used in the 0 to 1%, based on the total weight of the water in the composition. The polymers prepared by the process of the invention are useful in applications, such as in hot melt adhesives, hot melt sealants / fillers, plastic additives, compatibilizers, textile binders, roof mastics, traffic pints, barrier coatings. or protectors, powder coatings, water resistant sealers for wood and masonry materials, floor waxes, water repellents for textiles, polymers carrying biocides or other active ingredients in agricultural products. For use in the above coatings applications, the polymer can be formulated with materials such as binders, pigments, additives and fillers, to prepare coating compositions suitable for each application. The coating composition is then applied to a substrate and then dried. This coating composition can be applied by spraying, immersion or other methods known in the art. Suitable substrates include vinyl, polypropylene, metal, wood, cement, paper, nonwovens, textiles and other substrates known in the art. The coating composition can be dried under ambient conditions. The forced air can be used to aid in the drying of the coating composition. The heat can also be used in the drying of the coating composition. This forced air can be heated or the coated substrate can be placed in a heated oven., The oven temperature can vary from 35 to 110 ° C.

The polymers of this invention may also be useful as dry powder coating compositions. For these dry powder coating compositions, the polymer is isolated as a solid by the techniques described above. The dried polymer can be milled to a powder by any suitable milling equipment to produce particles in a size ranging from 0.1 to 50 microns, more preferably from 0.25 to 35 microns and especially preferred from 0.5 to 25 microns. The particle size can be measured in a Coulter ™ LS light scattering particle size analyzer. Suitable mills are friction mills, fluid mill -energy, colloid mills, vibratory ball mills (vibro-energy mills), pin mills, ball mills, roller mills and autogenous and semi-autogenous mills. Similarly, a combination of mills can be used to possibly increase the speed, where the first mill reduces the particle size, for example, to 100 to 1000 microns, and the second mill reduces the particle size further to the desired range. An example would be the initial use of a hammermill, followed by a semiautomatic mill, such as the Dyno-Mill ™ from CB Mills Inc (Buffalo Grove, 111.). The dry powder can be applied to a substrate, heated to form a film and cooled. Suitable substrates include vinyl, polypropylene, metal, wood, cement, paper, nonwovens, textiles and other substrates known in the art. The dry powder of the polymer can be heated to temperatures ranging from 60 to 150 ° C, to form a film. This film can then be cooled by storage at room temperature or by the use of forced cooling. The polymer can also be useful as an adhesive. Pair of adhesive applications, a first substrate coated with the polymer is formed by applying this polymer to a substrate, such as vinyl, polypropylene, metal, wood, cement or paper. The polymer may be in the form of a liquid or a solid. For a solid polymer, the polymer is then heated to the melting point of the polymer. A second substrate can then be applied to the first substrate coated with the polymer. The second substrate can be selected from vinyl, polypropylene, metal, wood, cement, paper or release paper. This polymer is then dried or cooled. The polymer can be dried under ambient conditions. The forced air can be used to aid in the drying of the coating composition. The heat can also be used in the drying of the coating composition. The forced air can be heated or the coated substrate can be placed in a heated oven. The oven temperature can vary from 35 to 110 ° C. The polymer can be cooled or stored at room temperature or by the use of cooled forced air. The following examples attempt to show the polymer of the invention, alternate processes for preparing the polymer of the invention, and the utility of this polymer of the invention in various applications. The following abbreviations are applied in the examples: SWM 1 = Unilin ™ 550MA (methacrylate C40 (average)) SWM 2 = Unilin ™ 550A (acrylate C50 (average)) SWM 3 = Unilin ™ 700MA (methacrylate C50 (average)) SWM 4 = Unilin ™ 700A (C50 acrylate (average)) SWM 5 = Unilin ™ 350A (C25 acrylate (average)) SWM 6 = Unilin ™ 350MA (methacrylate C5 (average)) SWM 7 = Unilin ™ 425A (acrylate C35 (average)) SWM 9 = Unithox ™ 450A (acrylate C30 (average) -b- (CH2CH2O) 10.5 (average)) SWM 10 = Unithox ™ 450MA (methacrylate C30 (average) -b- (CH2CH20)? Os (average)) DISP = Unilin ™ 450-ethoxylate DISP = Unilin ™ 550-ethoxylate IBOMA = isobornyl methacrylate Preparation of the Polymer, with the Use of Process 1 (Solution / Aqueous paste). A mixture of 75.0 grams of SWM 4 and 131.3 grams of heptane was heated to form a solution. The solution was stirred magnetically and allowed to cool. During cooling, the SWM crystals precipitated from the solution. When the temperature had dropped to 50 ° C - 60 ° C, 150.0 grams of butyl acrylate were added. The temperature of the solution dropped to 40 ° C. Then one hundred and fifty grams of methyl methacrylate were added to the solution. The temperature of the solution dropped to 30 ° C. The mixture was allowed to cool to room temperature to give an easily stirrable aqueous paste. An initiator solution was prepared using 6.3 grams of Lupersol 575 (t-amylperoxy 2-ethylhexanoate) and 26.6 grams of heptane. A 25.3 gram portion of the monomer slurry and 39.2 grams of heptane were metered into a 1-liter, 4-necked flask equipped with an agitator C, thermal couple, N2 inlet, and separate feed lines for the aqueous monomer paste and the initiator solution. This mixture was stirred with a N2 cover and heated until a moderate reflux began at about 85 ° C. A 2.1 gram portion of the initiator solution was then added. A clear, pale yellow solution was produced. After holding for ten minutes, simultaneous charges of the aqueous monomer slurry and initiator solution were initiated and sufficient heat was applied to maintain moderate reflux of the solution. After three hours, a total of 269.1 grams of the monomer aqueous paste had been fed and the temperature had reached 102 ° C. Both charges were stopped for 15 minutes, then the rest of the initiator solution was fed in 25 minutes. Following a 15 minute hold, the mixture was allowed to cool to room temperature. The polymer crystallized to give a crumbly solid, which was 65% polymer, 35% heptane. A portion of this solid was dried under vacuum at room temperature to give net pieces of polymer. Alternatively, a 65% portion of solid material was diluted to approximately 30% solids with additional heptane, reheated to form a clear solution, then cooled to 7 ° C with stirring, vacuum filtered and air dried in a Buchner funnel, to give solid polymer pieces, similar to those obtained by vacuum drying the 65% solid material. Preparation of the Polymer by Process 2 (Suspension polymerization) To 0.75 g of NaH2P0.2H20 in a 4-neck flask, with a capacity of 500 ml, were added 100.0 g of deionized water and 3.75 g of a 22.5% aqueous solution of dispersant (EM-2B (sodium salt of methacrylic acid copolymer) to give a clear solution, with a pH of 6.7 To the clear solution, then 32.0 g of butyl methacrylate and 10.0 g of SWM 1 were added. This mixture was stirred slowly with N2 sweep and heated to a moderate reflux until SWM 1 melted and dissolved to obtain an almost clear solution, then cooled to 56 ° V. A solution of 0.53 g of 95% Lupersol 575 in 8.0 g of butyl methacrylate was then added The stirring rate was increased and the mixture was reheated at 95 ° C for 10 minutes The solution was stirred at that temperature for 2 hours, then allowed to cool The polymer beads were collected by filtration , they were rinsed with desio water and allowed to dry at room temperature. Characterization of the globules: The percentage of solids (30 minutes @ 150 ° C) flows from 99.1 (average). The actual yield of the polymer solids was 48.9 g or 97.7% of the theory. The residual acrylic monomer was 2969 ppm BMA, as determined by Gas Chromatography ("GC"). The solids portion of the tetrahydrofuran-soluble polymer at room temperature was 78%. The pellets flowed together to form a film, when heated to 150 ° C. The DSC of the polymer showed a Glass Transition Temperature ("Tg") of 28 ° C and a single melt temperature of 67 ° C.

The latter was an indication that the SWM was uniformly incorporated into the acrylic polymer.

Preparation of the Polymer by Process 3 (Solution) A one-liter reaction vessel was equipped with a thermal pair, a temperature controller, a purge gas inlet, a reflux condenser cooled with water with purge gas inlet, an agitator, an addition funnel with Insta-Therm jacket, and an addition funnel without a jacket. To the addition funnel, without jacket, the Monomer Mixture 'A' was fed, which contained 316.34 g of a homogeneous mixture of 122.50 g of butyl acrylate. (purity 100%), 192.76 g of methyl methacrylate (99.85% pure), 0.70 g of Lupersol 575 and 0.35 g of dedecyl-mercaptan. To the jacketed addition funnel, which was heated to and maintained at 90 ° V to 100 ° C, Monomer Mixture 'B' was fed, which contained 56.88 g of a homogeneous mixture of 43.76 g of SWM 4 (purity 80.0%) and 17.50 g of toluene. Ten percent (31.63 g) of the 'A' Monomer Mixture, 10 percent (6.13 g) of the 'B' Monomer Mixture, and 87.50 g of toluene, were fed to the reaction vessel, which was then flooded with nitrogen for 30 minutes, before applying heat, to bring the contents of the reaction vessel to 95 ° C. When the contents of the vessel reached 95 ° C, the remainder of both Mixtures of Monomers 'A' and 'B' were fed continuously to the reaction vessel in 60 minutes. At the end of the addition of the monomer mixture, the contents of the reaction vessel were maintained at 95 ° C for 30 minutes. At the end of the 30 minute retention period, the polymerization temperature increased to 100 ° C before starting a charge containing 1.40 grams of Lupersol 575 and 35.00 g of toluene. The load was added evenly in a period of 60 minutes. At the end of the load, the batch was kept at 100 ° C for 60 minutes. At the end of the 60 minute retention period, vacuum was applied and the toluene was removed from the batch. This batch was finally subjected to a vacuum of 25 mm Hg at 120 ° C for 1 hour. The product, itself formed, exhibited a polymer solids content of 97.8% by weight (by GPC) and a molecular weight (Mw) of 341,000.

Preparation of the Polymer by Process 4 (Batch Dispersion Polymerization) The SWM 2 (25 grams) was dissolved in 75 g of styrene at 80 ° C to 85 ° C. After the solution became uniform, 150 g of butyl acrylate, reheated to 80 ° C, was added to the solution. The mixture was stirred to keep it uniform. In a separate vessel, 200 grams of deionized water and 2.5 grams of an aqueous solution of 60% Rhodapex surfactant C0436 were heated to 90 ° C. The monomer solution was added to the water / surfactant solution and homogenized at 15,000 rpm for several 30 second off-ignition cycles, until the monomer emulsion became thick. While preparing the above monomer emulsion, 800 g of deionized water was heated to 80 ° C in a 3 liter round bottom flask, with a condenser, -a thermal pair, a mechanical stirrer and a nitrogen gas inlet, to supply a positive pressure of nitrogen flow in the upper space of the reactor. The hot monomer emulsion was emptied into the reactor, followed by the addition of 0.7 g of t-butyl peroctoate. The reaction mixture was kept at 80 ° C for 4 hours, while stirring. At the end of the reaction, the mixture was cooled to room temperature.

Preparation of the Polymer by Process 5 (Polymerization of the Semi-continuous Dispersion) The SWM 5 (60 grams) and the polyethylene-b-polyethylene oxide dispersion aid, DISP 1 (6 grams) were mixed together and heated to melt. Under agitation, a mixture consisting of 528 g of butyl acrylate, 12 g of methacrylic acid and 3 g of n-dodecyl mercaptan, were then added to the mixture of SWM 5 and DISP 1. The solution was heated to 85 ° V and stirred until uniform- In a separate container, 600 g of deionized water and 21.4 g of the aqueous solution of the surfactant at 28% (sodium lauryl sulfate), were heated to 90 ° C. The hot monomer solution and the water solution and the customer surfactant were mixed and homogenized at 15,000 rpm for several 30 second on-off cycles until the monomer emulsion became thick. After the monomer emulsion was cooled below 40 ° C, under moderate agitation, 2 g of t-butyl peroctoate was added to the monomer emulsion and stirred for at least 10 minutes.

While preparing the above monomer emulsion, 200 g of deionized water was heated to 85 ° C in a 3-liter round bottom flask, with a condenser, a thermal pair, a mechanical stirrer and a nitrogen gas inlet, to supply a positive pressure of nitrogen flow in the upper space of the reactor. Half of the monomer emulsion was added to the reactor. The mixture was allowed to react for 30 minutes. Then the second half of the monomer emulsion was gradually added into the reactor through a pump in the reactor, in 2 hours. After completing the monomer emulsion charge, the reaction mixture was maintained at 85 ° C for 1 hour and then cooled to room temperature.

The following compositions were prepared by the processes described above.

Sample Composition Obtained by the Process 1 1 DISP 1/2 MAA7 88 BA / 10 SWM 5 5 2 1 DISP 1/2 MAA / 88 EHA / 10 SWM 5 5 3 1 DISP 2/29 IBOMA / 2 MAA / 59 BA / 10 SWM 2 5 30 Sty / 60 BA / 10 SWM 1 4 * 323Sty / 67BA 4 Sty / 59 BA / 1 MAA / 10 SWM 1 4 Sty / 73 BA / 2MAA / 10 SWM 1 4 40 Sty / 5 MMA / 10 BA5 MAA / 40 SWM 2 4 Sty / 30 MMA / 20 BA / 25 SWM 2 4 26 Sty / 52 BA / 2 MAA / 20 SWM 2 4 1 20 Sty / 58 BA / 2 MAA / 20 SWM 2 4 29 Sty / 59 BA / 2 MAA10 SWM 9 4 * 88.9 BA / 11.1 AA 3H 80 BA / 10 MAA / 10 SWM 1 3H 80 BA / 10 MMA / 10 SWM 1 3H 78 BA / 10 MMA2 AA / 10 SWM 1 3H 83 BA / 10 MMA / 2 AA / 5 SWM 1 3H 83 BA / 10 MMA / 2 AA / 5 SWM 3 3H 83 BA / 10 MMA / 2 AA / SWM 10 3H 83 BA / 10 MMA / 2 AA / 5 SWM 6 3H * 40 BA / 60 MMA 3 * 35 BA / 65 MMA 3 * 30 BA / 70 MMA 3 * 25 BA / 75 MMA 3 40 BA 55 MMA / 5 SWM 4 3 35 BA / 60 MMA / 5 SWM 4 3 30 BA / 65 MMA / 5 SWM 4 3 50 BA / 40 MMA / 10 SWM 4 3 45 BA / 45 MMA / 10 SWM 4 3 40 BA / 50 MMA / 10 SWM 4 3 35 BA / 55 MMA / 10 SWM 4 3 30 BA / 60 MMA / 10 SWM 4 3 50 BA / 30 MMA / 20 SWM 4 3 45 BA / 35 MMA / 20 SWM 4 3 40 BA / 40 MMA / 20 SWM 4 3 35 BA / 45 MMA / 20 SWM 4 3 30 BA / 50 MMA / 20 SWM 4 3 40 BA / 60 SWM 4 3 * 40 BAO SWM 2 3 * 40 BA / 60 SWM 7 3 * 40 BA / 60 SWM 5 3 60 BA / 40 SWM 7 3 60 BA / 40 SWM 5 3 80 BA / 20 SWM 7 3 80 BA / 20 SWM 5 3 46 * 45 BA / 55MMA 3 47 47 BA / 43 MMA / 10 SWM 1 3H 48 10 Sty / 33 MMA / 47 B A / 10 SWM 2 4 49 * 40 BA / 60 SWM 8 3 50 60 BA / 40 SWM 8 3 51 80 BA / 20 SWM 8 3 52 90 BA / 10 SWM 8 3 53 90 BA / 10 SWM 5 3 54 90 BA / 10 SWM 7 3 55 80 BMA / 20 SWM 1 2 56 80 BMA / 20 SWM 1/1 nDDM 2 57 60 BMA / 40 SWM 1 2 58 60 BMA40 SWM 1/1 nDDM 2 59 60 BMA / 40 SWM 1/2 nDDM 2 * = Comparative Example SWM = synthetic wax monomer H = Heptane replaces toluene, reaction operated at 90 ° C Adhesive Test An ASTM tape test was used to determine adhesion (D 3359-90). The substrates were the thermoplastic polyolefin (TPO): Dexter D / S 756-67 and the polypropylene (PP): Himont SB 823. Plates were cleaned by rubbing moderately with isopropanol. The samples were dried in a room at constant temperature for one week, before the adhesion test. The results are shown in Table 1.

Table 1 Sample TPO PP 47 5 4.5 5 * 0 1 2 2 * = Comparative Example 5 = great adhesion, 0 = no adhesion The above data shows that the polymers of the invention are useful as adhesives, even on substrates where good adhesion is usually difficult to obtain.

Water Repellents for Non-Woven Products and Textiles The polymer compositions of this invention were used as binders in formulations for treating fabrics. The polymers were added to the formulations at 10% by weight. The formulations were filled on a Birch Brothers filler at a pressure of 0.17 MPa and a speed of 8 meters per minute. The aggregate binder was 6% by weight. The samples were dried in a Mathis oven at 150 ° C for 4 minutes. The dried samples were evaluated using Test Method AAT 22-1980, Water Repellency Spray Test. Results are shown in table 2.

Table 2 Sample Classification Control (without filled formulation) 0 48 80 11 70 The above data indicates that the polymers of this invention are useful as water repellents in nonwovens and textile applications.

Wax Replacement in Floor Polishing Tests The following floor polishing formulation was used to test the polymer composition of the invention. The ratio of acrylic binder / alkaline resin swell / wax in this formulation is 75/10/15. An equal weight of the composition of the polymer of the invention replaced commercial waxes Epolene® E-43N and Poly Emulsion®325N35. For the control sample without wax, the Rh-oplex 1421 level was increased on an equal weight basis to count for the removal of Epolene® E043N and Poly Emulsion®325N35.

Material in Addition Order Percent in Weight Water 30.73 Kathon®CG / lCP 0.03 Acrysol®644 (42%) 5.52 Fluorad® FC-129 (50%) 0.02 Diethylene glycol -ethyl ether 5.78 Tripropylene glycol methyl ether 1.02 Rhoplex®1421 (38%) 45.76 Epolene® E-43N (40%) 4.35 Poly Emulsion 324N35 (35%) 4.97 SE-21 0.02 The floor polish was coated on black vinyl (B.V.) for the laboratory brightness test and on a black vinyl composition slab (B.V.C.) for the black mark laboratory tests of heels and foot drag marks test. The flooring test was done on commercial vinyl floor slabs.

Tests of Black Mark of Heels and of Resistance to stripes by the dragging of the feet. The laboratory test is described in the brochure Chemical Specialty Manufacturers Association Bulletin No. 9-73 with rubber shoe heels instead of rubber pails. The classification scale was from 1 to 10, with 10 being the best performance. The floor test was evaluated on marks made by pedestrian traffic in commercial buildings.

Static Friction Coefficient (S: C: Q: F): The S.C.O.F. was determined by the James friction test machine, based on an average of four readings. Brightness: - Brightness was determined by the method of ASTM D1455.

The results of the tests, described above, are shown in Tables 3 and 4. Table 3 Sample Size of Glitter Black Mark Striped S.C.O.F Particles 4 257 10/41 6 4, light 0.83 was from PE * 150 16/59 8 7 0.54 Without wax * NA 18/52 6 5 0.90 PE Wax / No Wax = Comparative Examples NA = Not analyzed Table 4 Sample T.P. B: V: B: V: C: Striped Black Mark S.C.O.F. 12"240 69/89 19/49 5 6 0.78 11 375 39/73 11/41 7, slight 7 0.72 9 326 18/42 7/29 5 9 0.77 10 351 16/44 7/30 5, slight 6 0.74 8 418 9/31 3/17 6 9 0.74 PE * 150 76/90 19/49 9 8 0.64 TP = particle size (nm) BV = black vinyl gloss 20 ° / 60 ° BVC = gloss of the black vinyl composition 20 ° / 60 ° * = comparative example Samples 4, 11 and 12 were also tested in a high traffic corridor that had been polished with a polish UHS Tan Buffer Pad on a polishing machine propane floors at 2000 rpm, periodically. The results are shown in Tables 5 and 6.

Table 5 Sample B.l. Luster 1 week 2 weeks 3 weeks Rayado B.M. 4 21/65 64 26/46 47/73 54/55 8 9 ~ PE * 30/69 91 23/34 27/68 42/51 B.l. = initial gloss 20 ° / 60 ° Luster = polished gloss at 20 ° / 60 ° 1 week = gloss at 20 ° as is / glossy B.M. = black mark 2 weeks = gloss at 20 ° / 60 ° polished 3 weeks = gloss at 20 ° polish 1 pass / 4 passes Table 6 Sample Luster 1 week 1 week * 2 weeks 2 weeks * Rayado 12 8 87 53 6 9 10 8/7 11 5 (nebulous) 64 26 7 9 16 8/7 PE * 9 91 54 8 9 12 9/8 B.l. = initial brightness 20 ° / 60 ° Luster = polished gloss at 20 ° / 60 ° 1 week = gloss at 20 ° / 60 ° 1 week * = gloss at 20 ° / 60 ° polished after 1 week 2 weeks = gloss at 20 ° / 60 ° after 2 weeks 2 weeks = gloss at 20 ° / 60 ° polished after 2 weeks Scratched = scratched after 1 week / 2 weeks The above data demonstrate that the compositions of this invention responded well to the luster of floors, due to their crystallinity.

Dry Powder Coating Compositions of polymers of this invention were tested in the utility as powder coating compositions. The polymers were milled using a Science Ware Micro Mill ™ mill. One gram of each dry polymer powder was placed in an aluminum weighing container. The remainder of each dry polymer powder was stored in a jar at room temperature. Samples at room temperature were checked to see if a free-flowing powder remained after 24 hours of storage. The samples in the weighing vessels were placed in an oven at 120 ° C, 140 ° C and 150 ° C, to determine at what temperature and time the dry polymer powder forms a film. For dry polymer powder coatings, a film forming temperature in the range of 120 to 150 ° C is acceptable, but the time to form a film is preferably less than 3 hours. The results of powder stability and time to form a film are shown in Table 7.

Table 7 21 '> 3 hours 2.5 hours NT * Good > 3 hours 2.5 hours NT * Good > 3 hours > 3 hours 2.5 hours * Good > 3 hours > 3 hours 2.5 hours Good > 3 hours > 3 hours 2.5 hours Good > 3 hours > 3 hours 2.5 hours Good > 3 hours > 3 hours > 3 hours S < 0.5 hours NT NT Good 1 hour NT NT Good 1.5 hours NT NT Good > 3 hours 1.25 hours NT Good > 3 hours > 3 hours 2.5 hours Good 0.75 hours NT NT Good 0.75 hours NT NT Good 0.75 hours NT NT Good 1.75 hours NT NT Good 1.75 hours NT NT Good < 0.5 hours NT NT Good < 0.5 hours NT NT Good < 0.5 hours NT NT Good < 0.5 hours NT NT Good < 0.5 hours NT NT 43 T NT NT NT 44 T NT NT NT 45 T NT NT NT 55 NT NT < 0.5 hours 56 S NT NT < 0.5 hours 57 G NT NT < 0.5 hours 58 G NT NT < 0.5 hours 59 G NT NT < 0.5 hour Good = free-flowing powder after 24 hours of storage S = slightly sticky, free flow not so much as in Good T = sticky, did not form a dry polymer powder NT = not tested * = comparative example The above data indicates that the polymers of this invention are useful as dry powder coating compositions. Some of the properties of the polymers of this invention were compared with polymers with more than 50 weight percent incorporation of the synthetic wax monomer. The data is shown in Table 8.

Table 8 Sample / Classification SWM / BA C2Q C25 Q5 C40 C50 60/40 49 / P 41 / P 40 / P 39 / P 38 / P 40/60 50 / T 43 / S 42 / P 57 / P * NT /80 51 / T 45 / T 44 / S 55 / P * NT /90 52 / T 53 / T 54 / NT NT NT SWM / BA = weight ratio of synthetic wax monomer to butyl acrylate P = stable, non-sticky powder, film formation a 120 ° C * film formation tested at 150 ° C = sticky, dust could not be obtained S = slightly sticky, difficult to obtain NT powder = not tested. The above data demonstrate that polymers with more than 50 weight percent incorporation of the synthetic wax monomer form dry, non-tacky powders, regardless of the length of the carbon chain in the synthetic wax monomer. This synthetic wax monomer is significantly more expensive than butyl acrylate and other monomers incorporated in the polymers of this invention. Therefore, it is desirable to reduce the amount of the synthetic wax monomer below 60 weight percent without sacrificing the properties of the dry powder polymer. The above data shows that the properties of the dry powder polymer at 60 percent incorporation of the synthetic wax monomer can be retained with 40 percent incorporation by increasing the length of the carbon chain in the synthetic wax monomer. The data suggest that it may be possible to reduce the incorporation of the synthetic wax monomer between 10 and 20 weight percent, without sacrificing the properties of the polymer powder.

Hot Melt Mass Sealant The polymer compositions of this invention were tested as hot melt sealants, applying the solid polymers to glass and vinyl substrates. The samples were heated in an oven 80 ° C, 90 ° C and 115 ° C. The heated polymers were checked to see how well they melted at each temperature. A nylon screen was applied on each molten polymer. The polymer was cooled and tested on the adhesion with an Instron machine that pulls the screen away from the substrate coated with the polymer. The results are shown in Table 9.

Table 9 13 * Po re Po re NT NT 14 Poor Poor Partial 214-321C A 15 Partial Good Good 5A C 16 Partial Partial Good 18 - 36 AA 17 Partial Good Good 125-143C C 18 Poor Partial Good 179-250 CA / C 19 Partial Partial Good NT C 20 Good Good Good 71A NT = not tested A = adhesive failure C = cohesive failure The above data indicates that the polymers of this invention are useful as hot melt sealants.

Wood Treatment The polymer compositions of this invention were applied to wood boards and tested in utility as water repellents for wood applications. Sapwood boards in correspondence, measuring 1.8 x 1.8 x 1.8 m (tangential x radial x longitudinal) were used in this test. The wood was clear, cut flat, straight grain, with 6 to 10 rings per 2.5 cm and 40 to 50% of summer sapwood. Samples were cut with a fine tooth saw to obtain as smooth a surface as possible. The polymer compositions and the control wood treatment compositions were applied to the wood boards by pressure treatment. For each level (percent by weight) of the tested coating composition, two wood boards were coated with the polymer of this invention. The coated wood was dried for two weeks. The samples were conditioned for 10 days at a relative humidity of 45%. The weights of the samples were checked until they were constant, to ensure moisture balance. The samples were weighed to approximately 0.001 grams. These samples were tested using a Dynamic S ellometer apparatus that records the swelling in thousandths of an inch. The instrument automatically measures the swelling values during the test. Samples were measured (radial, tangential, longitudinal dimensions) using a micrometer and measurements were recorded. The samples were placed radially in a swelling chamber and secured so that flotation did not occur during the test. These samples were then covered with distilled water and tested for 100 minutes. Immediately after the test, the samples were removed and weighed approximately 0.001 gram. The samples were again measured (radial, tangential, longitudinal dimensions), using a micrometer and these measurements were recorded. The Water Repellency Efficiency ("WRE") was measured by means of the following formula: A - B% WRE x 100 A A = Control Swelling Value, 10 or 100 minutes B = Swelling value of the polymer of the invention, 10 or 100 minutes. The first wooden board was tested 4 times. The second wooden board was tested 2 times. The results of the tests were averaged. These results are shown in Table 10. Table 10 Wax * 0.6 87 51 CCA / Wax * 0.6 / 0.6 83 53 1 72 41 2.5 91 59 5 82 44 1 -32 $ -37 $ 2.5 77 35 5 93 70 * = comparative example CCA = copper-chrome arsenate% = suspected experimental error. The above data shows that the polymers of this invention provide good water resistance and are suitable for wood treatment applications.

Claims (10)

1. CLAIMS 1. A polymer comprising, as polymerized units: A) from 1 to less than 50 weight percent of a synthetic wax monomer, of the formula I: where Rx is selected from H and CH3, R2 is selected from H and Ci-C5 alkyl, R3 is selected from H and CH3, n = 9-115, preferably 12-90, more preferably 15-50 and m = 0-1370, preferably 0-65, more preferably 0-50; and B) from 50 to 99 weight percent of at least one second monomer.
2. 2. The polymer according to claim 1, wherein the synthetic wax monomer of the formula I is present from 3 to 45 weight percent and this at least one second monomer is present from 55 to 97 weight percent.
3. 3. The polymer according to claim 1, wherein the synthetic wax monomer of the formula I is present from 4 to 40 weight percent and this at least one second monomer is present from 60 to 96 weight percent.
4. 4. The polymer according to claim 3, wherein said at least one second monomer is selected from (meth) acrylic acid, esters of (meth) acrylic acid, (meth) acrylic amides, aromatic vinyl monomers, substituted ethylene monomers , functional monomers with a rear crosslinking group, multifunctional monomers and their mixtures.
5. 5. A method for preparing a polymer, this method comprises: i) forming an aqueous paste by cooling a solution containing a synthetic wax monomer and a solvent; ii) forming a reaction mixture by mixing at least one second monomer with the aqueous paste; and iii) polymerizing the reaction mixture, in the presence of an initiator.
6. 6. A method for preparing a polymer, this method comprises: dissolving a synthetic wax monomer in at least one second monomer, to form a solution; mixing the water and at least one surfactant to provide a second solution; forming an emulsion of monomers, mixing the first and second solutions; supply a reactor with heated water; and polymerizing the monomer emulsion, adding this emulsion of monomers and at least one initiator to the reactor.
7. 7. A method of coating, this method comprises: applying a composition containing the polymer of claim 1, to a substrate.
8. 8. The method according to claim 7, wherein the synthetic wax monomer of the formula I is present from 3 to 45 weight percent and this at least one second monomer is present from 55 to 97 weight percent .
9. 9. The method according to claim 7, wherein the synthetic wax monomer of the formula I is present from 4 to 40 weight percent and this at least one second monomer is present from 60 to 90 weight percent . • »
10. 10. A method for using a polymer as an adhesive, this method comprises: forming a first substrate coated with polymer, applying the polymer of claim 1 to a substrate and applying a second substrate to the first substrate coated with the polymer.