Method of making hydrophobic copolymers hydrophilic

Abstract: A method for altering a macroporous cross-linked hydrophobic copolymeric lattice produced by precipitation polymerization in a solvent of at least one monounsaturated ester monomer and at least one polyunsaturated ester monomer soluble therein, in order to render the hydrophobic copolymeric lattice hydrophilic. The method involves saponifying the hydrophobic copolymeric lattice by reacting the surface of the hydrophobic copolymeric lattice with an aqueous alkali. The surface can also be rendered hydrophilic by polymerizing an acrylate monomer onto the lattice in order to form a surface containing carboxylic acid sites. The carboxylic acid sites formed on the surface of the lattice are converted to carboxylate anions.

Description: This invention relates to a method for altering the surface of a macroporous cross-linked hydrophobic copolymeric lattice in order to render the lattice hydrophilic. Two mechanisms for accomplishing this surface alteration are provided, along with copolymers produced by both mechanisms. One mechanism relates to the saponification of the surface, whereas the other mechanism involves carboxylation of the surface. In accordance with the present invention, polymer lattices are produced by novel processes not believed to be taught in the prior art. In general, the prior art relates to suspension polymerization processes for the production of porous polymeric and copolymeric spheres and beads in which the precipitant is present during polymerization. This is defined as an "in situ" process. What has been accomplished in the present invention, however, is a unique concept differing from the prior art methods and wherein hydrophilic post adsorbent powders are produced. In contrast to the post adsorbent materials heretofore known in the prior art, hydrophobic powders are treated in order to render the surfaces hydrophilic, thus rendering the powders of the present invention capable of adsorbing liquids having a high surface tension such as formamide, glycerol and water. The powders of the prior art have traditionally only been capable of adsorbing low surface tension liquids such as hexadecane, dioctylphthalate, bromonaphthalene, ethylene glycol and methyl iodide. For purposes of the present invention, high surface tension liquids are defined as those liquids having a surface tension generally in excess of about fifty-eight mNm⁻¹. This invention relates to methods for altering a macroporous cross-linked hydrophobic copolymeric lattice, produced by precipitation polymerization in a solvent of at least one monounsaturated ester monomer and at least one polyunsaturated ester monomer soluble therein, in order to render the hydrophobic copolymeric lattice hydrophilic. One method involves saponifying the hydrophobic copolymeric lattice by reacting the surface of the hydrophobic copolymeric lattice with an aqueous alkali. Another method involves polymerizing a hydrophilic acrylic monomer onto the surface of the hydrophobic copolymeric lattice in order to form carboxylic acid sites on the surface of the hydrophobic copolymeric lattice. The hydrophilic carboxylic acid sites may also be converted to more hydrophilic carboxylate anions. The invention provides a method of making a macroporous cross-linked hydrophobic copolymeric lattice and thereafter modifying the properties of said copolymeric lattice, wherein: (I) at least one monounsaturated ester monomer and at least one polyunsaturated ester monomer are together subjected to precipitation polymerisation by dissolving said monomers in a solvent therefor which is a non-solvent for the copolymer obtained therefrom, polymerizing said monomers in said solvent, and allowing said copolymeric lattice to precipitate therefrom as a powder particulate; and (II) the resulting hydrophobic copolymeric lattice is given an hydrophilic character: (i) by reacting the surface of said hydrophobic copolymeric lattice with an aqueous alkali, whereby said copolymeric lattice is saponified; or (ii) by polymerizing an acrylic monomer on the surface of said hydrophobic copolymeric lattice in order to form carboxylic acid sites on said surface, and, optionally, converting said carboxylic acid sites to carboxylate anions by reacting said surface containing said carboxylic acid sites with an aqueous alkali. The invention also provides an hydrophilic copolymeric lattice in powder form, obtainable by modification of a macroporous cross-linked hydrophobic copolymeric lattice, wherein: (I) said hydrophobic copolymeric lattice is obtained by precipitation polymerisation of at least one monounsaturated ester monomer and at least polyunsaturated ester monomer in a solvent therefor which is a non-solvent for the resulting copolymer, said precipitation polymerisation yielding said copolymer as a powder particulate; and (II) said hydrophobic copolymeric lattice is given an hydrophilic character by: (i) reacting the surface of said hydrophobic copolymeric lattice with an aqueous alkali to saponify said surface; or (ii) polymerizing an acrylic monomer on the surface of said hydrophobic copolymeric lattice, in order to form carboxylic acid sites on said surface, and, optionally, converting said carboxylic acid sites to carboxylate anions by reacting said surface containing said carboxylic acid sites with an aqueous alkali. In a preferred embodiment, the copolymer is in the form of a powder and the powder is a combined system of particles which can be defined as a lattice. The system of powder particles includes unit particles of less than one micrometre (micron) in diameter, agglomerates of fused unit particles of sizes in the range of from twenty to eighty micrometres (microns) in diameter and aggregates of clusters of fused agglomerates of sizes in the range of from two hundred to about twelve hundred micrometres (microns) in diameter. In one preferred embodiment of the present invention, the monounsaturated ester monomer is lauryl methacrylate, the polyunsaturated ester monomer is ethylene glycol dimethacrylate and the solvent is isopropyl alcohol. In the first mentioned method, the saponification is carried out with an alkali such as sodium hydroxide, potassium hydroxide and quaternary ammonium hydroxides, dissolved in aqueous alcohol. In the second method, the acrylic monomer which is polymerized on the surface of the hydrophobic lattice can be either acrylic acid or methacrylic acid. The resulting surface polymerized carboxylic acid sites may be converted to carboxylate anions by reacting the surface containing the carboxylic acid sites with an aqueous alkali. The aqueous alkali is preferably sodium hydroxide, potassium hydroxide or a quaternary ammonium hydroxide. The present invention also relates to hydrophilic macroporous cross-linked copolymers produced by either of the aforementioned methods. These and other objects, features and advantages, of the present invention will become apparent when considered in light of the following detailed description. The hydrophobic material, which is surface treated in accordance with the present invention and which functions as the basic starting material, has been employed as a carrier for active ingredients and can be broadly and generally described as a highly crosslinked hydrophobic polymer lattice. These materials are adapted to have entrapped and dispersed throughout and within the lattice, an active ingredient which may be in the form of a solid, liquid or gas. The lattice is in particulate form and constitutes free flowing discrete solid particles even when loaded with an active material. When loaded, the lattice may contain a predetermined quantity of the active material. The polymer has the structural formula: where the ratio of x to y is 80:20, R' is -CH₂CH₂- and R" is -(CH₂)₁₁CH₃. The hydrophobic polymer is a highly crosslinked polymer, as evidenced by the foregoing structural formula and is more particularly a highly crosslinked polymethacrylate copolymer. This hydrophobic material is manufactured by the Dow Corning Corporation, Midland, Michigan, U.S.A. and sold under the trademark POLYTRAP®. It is a low density, highly porous, free-flowing white particulate and the particles are capable of adsorbing high levels of lipophilic liquids and some hydrophilic liquids, while at the same time maintaining a free-flowing particulate character. In the powder form, the structure of the hydrophobic particulate is complex and consists of unit particles less than one micrometre (micron) in diameter. The unit particles are fused into agglomerates of twenty to eighty micrometres (microns) in diameter. These agglomerates are loosely clustered into macro-particles termed "aggregates" of 200 to 1200 micrometres (microns) in diameter. The following example illustrates one method for making a post adsorbed hydrophobic particulate polymeric powder suitable for use as the basic starting material for alteration by the surface treatment of the present invention. The hydrophobic powder produced in accordance with Example I is treated hereinafter to render the hydrophobic powder hydrophilic, as will be seen in Examples II-IV. EXAMPLE I A post adsorbed hydrophobic porous polymeric powder using the precipitation polymerization technique was produced by mixing in a five hundred milliliter polymerization reactor equipped with a paddle type stirrer, 13.63 grams of ethylene glycol dimethacrylate or eighty mole percent and 4.37 grams of lauryl methacrylate or twenty mole percent. Isopropyl alcohol was added to the reactor in the amount of 282 grams. The monomers were soluble in the isopropyl alcohol solvent, but not the precipitated polymer. Other solvents that can be employed are toluene, cyclohexane or heptane. The mixture including 0.36 grams of catalytic initiator benzoyl peroxide, was purged with nitrogen. The system was heated by a water bath to about 60°C. until polymerization was initiated, at which time, the temperature was increased to about 70-75°C. for six hours, in order to complete the polymerization. During this time, the polymer precipitated from the solution. The polymerization produced unit particles of a diameter less than one micrometre (micron). Some of the unit particles adhered together providing agglomerates of the order of magnitude of twenty to eighty micrometres (microns) in diameter. Some of the agglomerates adhered further and were fused and welded one to another, forming aggregates of loosely held assemblies of agglomerates of the order of magnitude of two to eight hundred micrometres in diameter. The mixture was filtered to remove excess solvent and a wet powder cake was tray dried in a vacuum oven. A dry powder consisting of unit particles, agglomerates and aggregates was isolated. A portion of this hydrophobic powder was surface treated in order to render the powder hydrophilic in accordance with one of the procedures of Example II or Examples III-IV which are set forth below. It is important to understand that the method of Example I for the production of hydrophobic porous copolymeric particulate powder materials is characterized as a precipitation polymerization technique. In accordance with this technique, monomers are dissolved in a compatible solvent in which the monomers are soluble, such as isopropyl alcohol. Polymer in the form of a powder is precipitated and the polymer is insoluble in the solvent. No surfactant or dispersing aid is required. The materials produced are powders and not spheres or beads. The powder particulates include unit particles, agglomerates and aggregates. The solvent is subsequently driven off resulting in an empty powder particulate, adapted to be post adsorbed with a variety of other types of functional active ingredients. The "in situ" suspension polymerization process on the other hand, provides that polymerization be carried out in water and wherein the phase including the monomers, the active and the catalyst, form beads or droplets and that the polymerization occur within each bead. The monomers and the active are insoluble in the water suspending phase. A surfactant or stabilizer is required in order to prevent the individually formed beads and droplets from coalescing. The resulting beads, with the active material entrapped therein, include a substantially spherical outer crust or shell, the interior of which contains a macroporous structure. The bead is generally of the order of ten to one hundred micrometres (microns) in diameter and can be as large as one hundred-fifty micrometres (microns), depending upon the rate of agitation employed during the process. In order to demonstrate the methods of the present invention, Examples II-IV are set forth hereinafter, in which the hydrophobic powder material produced in Example I, was surface treated in order to render the hydrophobic powder hydrophilic. A first method is shown in Example II. A second method is set forth in Example III. Example IV describes an additional step that may be included in the method of Example III. References to hydrophobic powder in Examples II-IV refers to the powder material produced in accordance to a process exemplified by Example I. EXAMPLE II 5.0 grams of hydrophobic powder was refluxed and stirred with 10.0 grams of NaOH, 150 cm³ of butyl alcohol and 15 cm³ of water. After reflux for 4.5 hours, the product was filtered and washed four times with 100 cm³ of 1:1 isopropyl alcohol and water, once with butyl alcohol and once again with isopropyl alcohol. The powder was vacuum dried to constant weight. Scanning electron microscopic photomicrographs of the treated powder showed no visible change in aggregate structure compared to untreated powder. Electron spectroscopic analysis (ESCA) showed 6 atom % Na at the surface of the powder. Attenuated total reflectance infrared radiation analysis indicated the presence of carboxylate ion (1590 cm-1) in the treated powder. The treated powder was easily wetted by water and produced a viscous paste upon minimal mixing. By comparison, untreated powder was completely non-wetted by water. EXAMPLE III 2.5 grams of methacrylic acid was added to 25.0 grams of hydrophobic powder that had been suspended in a mixture of 100 cm³ toluene, 400 cm³ heptane and 0.275 grams 1,1'-azobiscyclohexanecarbonitrile. The mixture was flushed with N₂ and heated at reflux (104°C.) for 4 hours. The product was filtered, washed with isopropyl alcohol and dried under vacuum to a constant weight. Scanning electron microscopic photomicrographs of the powder showed no apparent change in aggregate structure. Electron spectroscopic analysis (ESCA) showed an enrichment of oxygen (26.4 atom % 0) at the surface of the powder compared to untreated powder (20.0 atom % 0). The product was wettable by water. EXAMPLE IV 5.0 grams of product from Example III was mixed with 2.0 grams NaOH dissolved in a mixture of 200 cm³ isopropyl alcohol and 50 cm³ water. The mixture was stirred for 10 minutes at 65°C. The powder was recovered by filtration, washed twice with 300 cm³ 1:1 isopropyl alcohol H₂O and dried under vacuum to a constant weight. Electron spectroscopic analysis (ESCA) showed the presence of 3.4 atom % Na on the surface of the powder. The powder was highly adsorbent toward water. Test data showing the hydrophilic nature of the materials produced by the methods of Examples II-IV are set forth in Table I. It should be apparent from Table I that the powder materials produced by both the method of Example II and the method of Examples III-IV are capable of adsorbing water, in contrast to the hydrophobic powder of Example I. Free flowing adsorption capacity was determined by addition of incremental amounts of liquid to a known amount of powder, using gentle mixing, until the powder was no longer free flowing. The capacity was expressed as: wt. Powder + Liquid - Initial wt. of Powder wt. Powder + Liquid X 100 The water adsorbing porous polymeric materials of the present invention are to be contrasted with the water containing beads of U.S. Patent No. 3,627,708, issued December 14, 1971. The bead of the '708 patent is produced by "in situ" suspension polymerization and is adapted to contain water only because of the presence of a solubilizer such as sodium bis(2-ethyl hexyl) sulfosuccinate. The material of the present invention, on the other hand, is produced by a precipitation polymerization process, which contains no solubilizer and produces a material in the form of a powder consisting of unit particles, agglomerates and aggregates. Thus, the materials of the present invention are very distinct from the materials of the '708 patent. The materials of the present invention are of general utility and may be used in any situation requiring the adsorption of aqueous systems.

Claims: A method of making a macroporous cross-linked hydrophobic copolymeric lattice and thereafter modifying the properties of said copolymeric lattice, wherein: (I) at least one monounsaturated ester monomer and at least one polyunsaturated ester monomer are together subjected to precipitation polymerisation by dissolving said monomers in a solvent therefor which is a non-solvent for the copolymer obtained therefrom, polymerizing said monomers in said solvent, and allowing said copolymeric lattice to precipitate therefrom as a powder particulate; and (II) the resulting hydrophobic copolymeric lattice is given an hydrophilic character: (i) by reacting the surface of said hydrophobic copolymeric lattice with an aqueous alkali, whereby said copolymeric lattice is saponified; or (ii) by polymerizing an acrylic monomer on the surface of said hydrophobic copolymeric lattice in order to form carboxylic acid sites on said surface, and, optionally, converting said carboxylic acid sites to carboxylate anions by reacting said surface containing said carboxylic acid sites with an aqueous alkali. A process according to claim 1, in which said powder particulate comprises unit particles of less than one micrometer (micron) in average diameter, agglomerates of fused unit particles of sizes in the range of from twenty to eighty micrometers (microns) in average diameter, and aggregates of clusters of fused agglomerates of sizes in the range of from two hundred to twelve hundred micrometers (microns) in average diameter. An hydrophilic copolymeric lattice in powder form, obtainable by modification of a macroporous cross-linked hydrophobic copolymeric lattice, wherein: (I) said hydrophobic copolymeric lattice is obtained by precipitation polymerisation of at least one monounsaturated ester monomer and at least polyunsaturated ester monomer in a solvent therefor which is a non-solvent for the resulting copolymer, said precipitation polymerisation yielding said copolymer as a powder particulate; and (II) said hydrophobic copolymeric lattice is given an hydrophilic character by: (i) reacting the surface of said hydrophobic copolymeric lattice with an aqueous alkali to saponify said surface; or (ii) polymerizing an acrylic monomer on the surface of said hydrophobic copolymeric lattice, in order to form carboxylic acid sites on said surface, and, optionally, converting said carboxylic acid sites to carboxylate anions by reacting said surface containing said carboxylic acid sites with an aqueous alkali. An hydrophilic copolymeric lattice according to claim 3, wherein said powder particulate comprises unit particles of less than one micrometer (micron) in average diameter, agglomerates of fused unit particles of sizes in the range of from twenty to eighty micrometers (microns) in average diameter and aggregates of clusters of fused agglomerates of sizes in the range of from two hundred to twelve hundred micrometers (microns) in average diameter.

Inventors: PARK WILLIAM ROBB ROY, ZIEMELIS MARIS JAZEPS, PARK, WILLIAM ROBB ROY, ZIEMELIS, MARIS JAZEPS
Applicants: DOW CORNING, DOW CORNING CORPORATION
Application year: 1990
Main classification: C08F8
IPC codes: C08F265, C08F8, C08F2