ALUMINUM ZIRCONIUM METALLO-ORGANIC COMPLEX USEFUL AS COUPLING AND HYDROPHOBIC AGENTS

Abstract: Novel compositions of matter which are mixed metal metallo-organic complex agents comprised of a chemically united complex aluminum moiety and a tetravalent zirconium moiety. The specific process for preparing such compositions in organic/solvent media with desirable hydrolytic stability is described. Further described are compositions of matter wherein the aforementioned metallo-organics are employed to chemically modify the surface of fibrous and particulate inorganic substances and certain organic particulates, thereby resulting in hydrophobic, organophilic fibers and particles having improved rheological properties which facilitate higher filler (fiber) loading levels and serve to enhance the physical properties of composite articles and coatings formed therewith.

Description: ALUMINϋM ZIRCONIUM METALIO-OPGANIC COMPLEX USEFUL AS COUPLING AND HYDROPHOBIC AGENTS TECHNICAL Firm AND RAf GPOTT T) ART This invention relates to the manufacture of composite products, such products to be defined as containing chemically dissimilar materials most generally typified by an organic nonpolar substance and an inorganic polar substance. Specifically, the invention describes the preparation and use of novel mixed metal metallo-organic substances which are useful in chemically modifying the particulate or fibrous materials, preferably inorganic materials, for incorporation into the resin matrices with which they will share an interfacial boundary. It is recognized by those skilled in the art that manufacture of mineral filled or fiber reinforced plastic or rubber articles offers unique problems associated with the poor wetting of the mineral or fiber by the resin. Subsequently, interfacial failure can occur and is augmented in most applications by the presence of moisture which migrates to the interface in the absence of any surface treatment of the mineral filler or fiber and will result in substantial loss in flexural and tensile strength properties. An identical problem is observed in analogous composite systems such as paints and coatings, paper, adhesives, sealants and other ∞iπpositions containing the organic/inorganic interface. Historically, fibers, most specifically fiberglass, have been treated with methacrylate chromic chloride as disclosed in: U.S. Pat. Nos. 2,273,040; 2,524,803; 2,552,910; 2,544,666; 2,554,667; 2,544,668; 2,611,718; and trialkoxy silanes as disclosed in: U.S. Pat. Nos: 2,742,378 2,776,910 2,832,754 2,930,809 2,946,701 3,045,036 3,169,884 3,211,684 3,258,477 3,849,471 Both of these materials impart additional dry and wet strength properties to glass reinforced fabricated articles. Silanes have also enjoyed usage as a preferred surface treatment for mineral fillers such as silica, alumina iarihydrate, mica, wollastonite, and glass beads when such are to be used in applications wherein physical strength of the composite is an important performance property. More recently, organo titanates, such as described in U.S. Pat. Nos. 4,096,110; 4,098,758; 4,141,751; and 4,152,311 have found some application in mineral filler thermoplastic composites. In other less demanding applications as are found in paper manufacture and some coating areas it is viable to use surfactants or fatty acid salts to chemically alter the inorganic substrate. The usefulness of silanes is offset by their high cost, requirement for heat input to react with fillers, and handling problems related to rapid hydrolysis and polymerization in the presence of moisture which greatly reduces their effectiveness. Titanates are also hindered by undesirable economics, albeit not as severe as silanes, and also by their limited application in aqueous environments and in products wherein strength properties are significant. The compositions to be described herein are unique substances which are highly soluble in water and a variety of polar organics, hydrolytically stable, cost effective viz-a'-viz aforementioned silanes and titanates, and highly reactive, reacting essentially instantaneously with mineral fillers and functional organic particulates at ambient temperature. The said compositions are predicated upon an important symbiotic relationship which recognizes the preferred reactivity of inorganic substrates with the aluminum portion of the molecule and the advantages of using a tetravalent transition metal for purposes of complexation with a reactive organic. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a reproduction of an infrared (IR) spectroscopy scan comparing the curves obtained from scanning unreacted propylene glycol (dotted lines) with sec-propanolato aluminum chlorhydrate (solid line) . Figure 2 is the IR scan for the reaction products of methacrylic acid and zirconium oxychloride. Figure 3 is the IR scan of the reaction product of methacrylic acid and complexed aluminum chlorohydrate. Figure 4 is the IR scan of the product of Example 2, infra*. Figure 5 is the IR scan of the reaction product of adipic acid and zirconium oxychloride (two phase) . Figure 6 is the IR scan of the reaction product of adipic acid and complexed aluminum chlorohydrate. Figure 7 is the IR scan of the product of Example 4, infra. Figure 8 is the IR scan of the product of Example 5, infra. Figure 9 is the IR scan of the produce of Example 6, infra. Figure 10 is the IR scan of the product of Example 7, infra. PISCQZURE OF THE INVENTION The subject invention pertains to compositions of matter which are the complex reaction products of (I) chelate-stabilized aluminum compositions, (preferably chelate stabilized aluminum chlorohydrates) , (II) zirconium oxyhalide (preferably oxychloride) , and (III) carboxylic acids. The reactants utilized to obtain the compositions of the present invention can generally be represented by the empirical formulae (I), (II), and (III): l2 ( ORιO ) aAbBc <■ ) ZrAdBe ( II ) 0-C=0 (III) wherein: A and B may be halogen, most preferably chlorine, hydroxy. Preferably A and B are chloro or hydroxy, a is a numerical value ranging frcm about 0.05 to 2, preferably 0.1 to 1, b is a number ranging from about 0.05 to 5.5, preferably about 1 to 5; and c is a number ranging from 0.05 to 5.5, preferably about 1 to 5, provided that 2a + b + c = 6 in the chelate stabilized aluminum reactant. Most preferably A is hydroxy and b ranges from 2 to 5, and B is chlorine and ranges from 1 to 3.8. The variables d and e have a numerical value from 0.05 to 4, provided that d + e = 4 in the zirconium oxyhalide metallo-organic complex reactant. Preferably there is at least one hydroxy group and one halogen group in the zirconium reactant. More preferably the empirical ratio of hydroxy to the zirconium in this group is from about 1 to 2, and the ratio of halogen to zirconium is about 2 to 3, in that reactant. In the aluminum containing segment of Formula I, pairs of aluminum atoms are joined by bidentate chelating ligands wherein: (1) -ORiO- is an. alpha, beta or alpha, gamma glyσol inwhich i is an alkyl, alkenyl, alkyπyl, or aralkyl group having from 1 to 6 carbon atoms, most preferably 2 to 3 carbon atoms, such ligands to be used exclusively or in combinations within a given composition, or (2) -ORiO- is an alpha-hydroxy carboxylic acid -0-CH(R3)-C0CH having from 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms (i.e. preferably R3 is H or CH3). In each instance the organic ligand is bound to two aluminum O PI atoms through two oxygen heteroatoms. The organofunctional ligand -OC(R2)0- is a moiety which can be derived from one of, or a combination of, the following groups: (1) an alkyl, alkenyl, alkynyl, aryl or aralkyl carboxylic acid having from 2 to 36 carbon atoms, the preferred range being 4 to 18 carbon atoms; (2) an aminofunctional carboxylic acid having from 2 to 36 carbon atoms, the preferred range being 4 to 18 carbon atoms; (3) a dibasic carboxylic acid having from 2 to 18 carbon atoms wherein both carboxy groups are preferably terminal, the preferred range being 2 to 6 carbon atoms, or; (4) acid anhydrides of dibasic acids having frcm 2 to 18 carbon atoms, the preferred range being 2 to 6 carbon atoms; (5) a mercapto functional carboxylic acid having frcm 2 to 18 carbon atoms, the preferred range being 2 to 6 carbon atoms; (6) an epoxy functional carboxylic acid having frcm 2 to 18 carbon atoms, preferably from 2 to 6 carbon atoms. An extensive variety of -OC(R2)0- anionic ligands is useful in the preparation of the subject compositions. Examples of specific dibasic acids include the anions of oxalic, malonic, succinic, glutonic, adipic, tartaric, itaconic, maleic, fumaric, phthalic and terephthalic and examples of specific monobasic acids include the anions of fatty acids, such as myristic, palmitic, stearic, oleic, linoleic and linolenic acids. In seme compositions, in accordance with the present invention, the hydrophobicity imparted by the fatty acids provides a preferred material. Examples of specific aminofunctional carboxylate anions, -OC(R2)0-, include the anions of glycine, alanine, beta-alanine, valine, leucine, isoleucine, phenylalanine, tyrosine, serine, threonine, methionine, cysteine, cystine, proline, hydroxyproline, aspartic, and glutaric acids. Examples of specific monobasic carboxylate anions. OMPI -0C(R2)O-, include the anions of acetic, propionic, butyric, pentanoic, hexanoic, heptanoic, octanoic, dodecanoic, πyristic, palmitic, stearic, isostearic, propenoic, 2-methylpropenoic, butenoic, hexenoic, benzoic and cinnammic acids. Examples of the anhydrides of dibasic acids include phthalic, isophthalic and terephthalic anhydrides. Examples of chelating ligands, -ORiO-, include ethylene glycol, propylene glycol, glycerol, etc. Exaπples of alpha-hydroxy acids, R3CH(0H)C0O-, are glycolic, lactic, alpha-hydroxybutyric, and tartaric acids and those known in the art. While not wishing to be bound by theory, characterization of these compositions using infrared spectroscopy (Figures 1 to 10) has indicated that greater than 99% (>70% where C12-QL8 carboxylates are used) of the organofunctional ligand, -OC(R2. )0- is present in complex form (i.e. has reacted) in the aluminum zirconium inetallo-organic, and furthermore, that the organofunctional ligands are bound to an aluminum metal center on the one hand and to a zirconium metal center on the other. The IR information also indicated that the chelating agent -ORiO- forms a chelated complex with aluminum. Thus, the reaction product apparently involves the chelated aluminum moiety bridged to the zirconium oxychloride moiety through the organofunctional ligand. This may be empirically represented by formula IV: [Al2 ( ORlO ) aa Bc]χ[OC ( 2 ) 0]γCZ r A < 3Be]z ( IV ) wherein A and B are as above-defined, and a,b,c,d and e are as above defined, except that, in order to form the bonds depicted, the substituents attached to the metal groups are appropriately reduced, i.e. 2a + b + c= 4 (2a + b + c = 5 when the aluminum moiety is a terminal group) , and d + e = 2 (d + e = 3 when zirconium moiety is a terminal group) . When the aluminum moiety or the zirconium moiety forms the terminus in the molecular chain, one of the A or B groups may be replaced by a lower alkoxy group having 1 to 6 carbon atoms. X, Y and Z are at least each 1, and may vary from 1 to 100 or more, depending on the reactivity of the particular materials and the desired form of the product. The molar ratio of aluminum moiety to zirconium moiety (X:Z) may vary from about 1.5 to 10, with the preferred ratio being from about 3 to 6. The ratio of organofunctional ligand to total metal (Y: (2X + Z)) may vary from about 0.05 to 2.0, with the preferred ratio being about 0.1 to 1.0. The composition cited herein is preferably not prepared in the absence of solvent to avoid encountering undesirable hydrolysis and polymerization reactions resulting in a highly polymeric solid reaction product. Preparation of the subject composition is preferably attained in solvents which may be comprised of lower alcohols having 1 to 6 carbon atoms and lower ketones having 1 to 6 carbon atoms, wherein the water content may vary frcm 0% to 25%. The active matter of compositions so prepared is from 10% to 60%, preferably frcm 15% to 50%. Pursuant to such preparation the product may be spray dried, freeze dried or otherwise solvent stripped to leave a solid having high activity. Broad classes of aluminum zirconium metallo-organic complexes may be prepared wherein the solvent composition may vary as previously defined. It has also been discovered that such complex compositions, when prepared in substantially water free organic solvent systems, are soluble in various non-aqueous solvents, and have properties such as coupling agents which are particularly advantageous in systems adversely affected by the presence of water. Thus, those hydrophobic embodiments of the present invention can be used as coupling agents for inorganic pigments, fibers or fillers in polymer systems which cannot effectively tolerate water or OMPI moisture, including polyolefins, various elastomers, epoxies, etc., or in water free systaπs such as solvent based paints, adhesives, caulks, coatings, etc., as well as many plastic products and forms, such as films, extruded or molded forms, etc., which are found substantially in the absence of water. The metallo-organic complex thus prepared is substantially hydrophobic, and is soluble in a wide variety of non-aqueous solvents. Suitable industrial solvents are well known, and include alcohols, ketones, carboxylic acids and their esters, tetrahydrofuran, dioxane, dimethylsulfone, dimethylformamide, dimethylacetamide, carbon tetrachloride, mineral oil, toluene, xylene and similar organic solvents. The present invention also provides a process.for preparing the compositions described above. Hydrolytically stable products having a shelf life in excess of 30 days can be prepared by cσplexation of the dimeric aluminum chlorohydrate moiety with a bidentate chelating ligand which imparts hydrolytic stability, such as an alpha, beta or alpha, gamma glycol having frcm 1 to 6 carbon atoms, the preferred ligands having 2 to 3 carbon atoms? or with an alpha-hydroxy carboxylic acid having 2 to 6 carbon atoms. Such cσmplexation should utilize a mole ratio of complexing ligand to dimeric Al of 0.05 to 2, the preferred ratio being 0.10 to 1.00. OSie stabilized aluminum complex can be prepared as either an isolated composition prior to introduction of the zirconium moeity in solvent solution or prepared in situ with zirconium oxychloride, the preferred route being preparation of the stabilized aluminum complex as a separate, isolated composition wherein the aluminum complex solution is dried to remove water and other solvents, and subsequently redispersed in nonaqueous media. Preferably the dimeric aluminum reactant is dissolved in methanol, whereupon propylene glycol is added and the mixture refluxed at 65-70°C for one hour to form the stabilized dimeric aluminum complex. Cσmplexation with -OC(R2)0-, the organofunctional ligand. OMPI IP can be achieved either upon introduction of the ligand to a solution containing only zirconium oxychloride, or after the introduction and reaction of the zirconium oxychloride with the aforementioned stabilized aluminum chlorohydrate. Said reaction shall employ a mole ratio of -OC(R2)0- to total metal of 0.05 to 2.00, the most preferred ratio being 0.10 to 0.50. The route elected for synthesis will result in a significant difference in end product composition as characterized by physical and compositional properties with each type of complex useful in particular types of applications. It is a further teaching of this invention that the basicity of the dimeric aluminum chlorohydrate moeity critically alters both the reactivity of such with the zirconium moeity and the resultant performance of the aluminum zirconium metallo-organic complex end product. It is understood here that basicity is defined in terms of a divalent Al reactant typified by the general formula: Al20HbCl c wherein b+c=6, basicity is equal to b/6. The basicity can be varied frcm 0 to 5/6 (0.83) by reaction of the aluminum chlorohydrate with a chloride source exemplified by, but not restricted to, HC1. Preparation of a reduced (less than 5/6) basicity dimeric aluminum chlorhydrate specie with invariant compositions occurs by careful comingling of the hydrochloric acid and aluminum chlorohydrate so as to maintain a constant temperature of 30°C to 00°C resulting from the exothermic addition, the preferred temperature being 40°C to 60°C. It is to be noted that maintenance of the exotherm temperature at less than 30°C requires an iitpractically lengthy addition time, whereas an exotherm temperature in excess of 60°C may result in variant composition. The reduced basicity product can then be reacted with the aforementioned bidentate ligands, -ORiO- and 10 -OCH(R3)C0O-, resulting in the following compositions: l2 ( RlQ2 ) aOHbClc or Al2 ( OCH ( R3 ) COO ) aOHbCl c where 2a + b + σ= 6. . In a typical preferred composition, following the reaction of equimolar quantities of hydrochloric acid and dimeric aluminum chlorohydrate, a = 1.00, c • * ■ * ■ 2.00, b = 2.00, and basicity is therefore 0.33. Compositions prepared in accordance with the teachings of the subject invention are characterized as having a slight yellow color which may range from <50 Pt-Co to Gardner 5 in intensity. Such compositions generally are clear immediately after preparation, but may contain as much as 0.5% insolubles which may be allowed to sediment or removed by conventional filtration techniques. The active product can be isolated by low vacuum ambient temperature solvent removal, thereby resulting in a highly viscous (>106 ςps) gelatinous mass that, upon complete drying, forms a rigid solid which adheres strongly to glass and resists aqueous dissolution. Another composition of matter of the invention is the reaction product of the aforanentioned aluminum zirconium metallo-organic complexes having the structure as previously described and finely divided inorganic mineral fillers, pigments and fibers. Thus, from 0.02 to 1.00 phf (parts per hundred filler) of the active product may be chemically reacted with the surface of a particulate inorganic material, such materials to include silica, calcium carbonate, alumina trihydrate, aluminum silicates (Kaolin and the like), talc, wollastonite, glass beads, mica or titanium dioxide resulting in an essentially immediate, largely irreversible alteration in the physical and chemical properties of such particles. On the other hand, dispersion of any of the foregoing particulate minerals in an organic medium in the absence of the composition of the present invention results in sharp viscosity increase, particle agglomeration, nonuniform distribution and poor wetting; treatment with the subject aluminum zirconium metallo-organics, either prior to or at the time of introduction of these particulates to the resinous organic medium results in observable improvements in all of these properties. Such improvements afford the use of significantly increased quantities of such mineral particulates while achieving a uniform dispersion of the mineral in the organic matrix. In the specific instance of such particulates being used in a resinous matrix, be it a thermoset thermoplastic or elastomer, the resultant fabricated article manufactured with such surface modified particulates will show an improvement in physical strength properties which is related to the capability of the finished article being able to transfer an applied stress across the resin particulate interface. It is an object of this invention that the interfacial void which characterizes an untreated filler in contact with a resinous matrix is largely eliminated when the mineral surface has been modified with the subject composition due to: 1. sizeable changes in the particulate surface energy thereby leading to enhancement of the wetting of the treated particulate by the resin; and 2. chemical bonding which occurs between the two dissimilar phases through the intermediacy of the aluminum zirconium metallo-organic, one end of which is attached to the particulate and the other end of which attaches to the resin. Specifically, the chemical nature of the mineral surface which is initially highly hydrophilic, organophobic is modified resulting in one which is highly hydrophobic and organophilic. Although discussion has focused upon the reaction between aluminum zirconium metallo-organic agents and inorgainc mineral fillers, it is a further object of the invention that such complex agents are useful in the modification of particulate 12 organics wherein the organic has pendant reactive groups, i.e. hydroxy or halogen substituents. Thus, by non-limiting example the subject composition can be employed to alter the surface of a substance such as tetrabrcmobisphenol A rendering it more readily dispersible in a resinous system and thereby enhance its efficiency as a flame retardant. While not wishing to be bound by theory, reaction of the aluminum zirconium metallo-organic agent is postulated to occur between the pendant hydroxy or other groups of both aluminum and zirconium metal centers and the filler substrate surface hydroxy groups or surface adsorbed molecules of water. The heretofore described modification of the filler surface can be readily effected by any of the following reaction modes: (1) Dissolution of the aluminum zirconium metallo-organic agent in a suitable solvent, such solvents to include water, lower alcohols or fatty alcohols, ketones, carboxylic acids and their esters, tetrahydrofuran, dioxane, halogenated (preferably chlorinated) hydrocarbons, such as carbon tetrachloride or methylene chloride, dimethylsulfoxide, mineral oil, toluene, oxylene and similar organic solvents, and subsequent addition of the mineral or organic filler (5 to 85 wt percent of total slurry) with concommitant mixing. (2) Direct addition of the aluminum zirconium metallo-organic agent to a pre ixed slurry prepared with any of the aforementioned solvents. Such slurries may contain frcm 5 to 85 wt percent filler. (3) Direct addition of the aluminum zirconium metallo-organic to the dry filler and high shear agitation such as provided by a Waring Blender to uniformly distribute the treating agent on the filler surface. (4) Direct addition of the aluminum zirconium OMPI metallo-organic to the resin with subsequent addition of the filler accompanied by high shear mixing as exemplified by a Waring blender. Other methods of contacting fillers with the compositions of the present invention will be apparent to those skilled in the art. Reaction between the filler substrate and the aluminum zirconium metallo-organic agent typically occurs within seconds after contact of the substrate and modifier as effected by low shear mixing (which may include manual agitation) for slurries having an initial viscosity of less than 50,000 cps. An abrupt viscosity reduction to less than 10% of the original viscosity is indicative of the significant change in the surface character of the filler. The above disclosed inorganic and organic fillers to be used in accordance with the present invention may broadly include particles ranging in size frcm 0.05 to 500 microns, preferably 0.5 to 50 microns. Where the composition is used with inorganic or organic fibers of filaments, they may also range from about 0.05 to 500 microns (equivalent cylindrical diameter) , preferably 0.05 to 50 microns. While some benefit will be obtained from the use of the present aluminum zirconium metallo-organic agents with inorganic or organic fillers of substantially any size, typically the improvement in properties is more substantial and more necessary with the smaller particles. Another composition of matter which is the subject of this invention is the reaction product of the subject aluminum zirconium metallo-organic agent and glass fibers either as strands in the forming operation or subsequently as woven fiberglass and woven or nonwoven fiberglass mat. The manufacture of fiberglass typically consists of passing the hot glass fibers as they emerge from the forming bushing through an aqueous sizing bath which includes antistatic agents, wetting agents, binders and, of primary importance in this discussion, coupling (or OMPI keying) agents. Such agents in the past have been typified by organosilanes and methacrylato chromic chloride. The subject composition has a capacity to chemically react with both the glass fiber and a resin (most commonly epoxy or unsaturated polyester) and being highly soluble and stable in aqueous media, therefore can be introduced as a replacement for either the silane and/or the methacrylato chromic chloride. Such substitution will impart to the fiberglass the reactivity necessary for successful use in fiberglass reinforced composites and also the necessary antistatic properties to facilitate handling during the manufacture of the fiberglass and its subsequent use in a variety of fabrication techniques (to include spray gun, hand lay-up, and other commonly encountered methods of fiberglass use) . It is a futher object of this invention that aluminum zirconium metallo-organic complexes wherein R2COO- has 14 to 36 carbon atoms are useful in iπparting a colorless, durable, water repellant finish to both paper, fiberboard, and textile substrates with performance comparable to, or superior to, the commercially available carboxylato C14-C18 chromic chlorides which are deep green in color. As detailed in the foregoing discussion, treatment of mineral or organic fillers and pigments, in accordance with the teachings of the subject invention, will permit the usage of elevated levels of such fillers in plastic and elastomeric articles without substantial diminution in physical properties of the finished article, with advantageous reductions in filled resin viscosity, and with attendant cost savings and property benefits. Also, similar treatment of mineral fibers (especially glass fibers) , and also carbon fibers will enhance performance of such in glass reinforced matrices. Additionally, the use of such treated fillers and pigments will permit the use of higher filler levels in paints, coatings, binders, sealants and paper manufacture while OMPI > maintaining product performance. Moreover, the infinite solubility and long term stability of the subject compositions in aqueous media and the rapid reaction with fillers or pigments at ambient temperature (60°F to 100°F) provides the manufacturers of such products with the opportunity to treat the fillers and pigments they use in situ without altering their manufacturing process or the option of using a pretreated filler with • comparable performance advantages. MODES FOR CARRYING OUT THE INVENTION EXAMPLE 1: PREPARATION OF REDUCED BASICITY SEC-PROPANQLATO ALUMINUM CHLOKOBYDRATE ' Muminum chlorohydrate, 1.14 moles Al (123.44g, 5/6 basic) is dissolved in an equal part of water. Subsequent to complete dissolution, concentrated hydrochloric acid, 112.84g, is slowly added to the reactor with agitation. The rate of addition is controlled so as to prevent the reaction exotherm from exceeding 50°C. The resulting product is aluminum chlorohydrate, basicity 1/2. Thereupon the reaction product is combined with 150g MeOH. The mixture is brought to reflux, and propylene glycol, 10.88g (0.143 moles) is fed to the reduced basicity aluminum chlorohydrate, and the systan refluxed for 1 hour. The product is indicated by infrared spectroscopy to have a complexed form of propylene glycol. The IR spectrum of propylene glycol (neat, broken line in Figure 1) shows three strong absorbance bands in the 1200-1360 αrr-1 region at 1230 cπrl, 1290 cm~l and 1330 cm~l. The latter two bands can be assigned with reasonable certainty to O-H bending vibration modes in the glycol. Upon co plexation, the O-H bond is destroyed resulting in the disappearance of such bands as clearly revealed in the spectrum of the propanolato aluminum (solid line). Moreover, the C- stretching vibrations and related overtone bands found at 840-1230 cπr-1 have either OMPI c disappeared or shifted, as seen in the spectrum of the complexed material. EXAMPLE 2: PREPARATION OF ALUMINUM ZIRCONIUM METALLO-ORGANIC COMPLEX Zirconium oxychloride solution, 0.0339 moles Zr (20.30g), is combined with 50.00g of isopropyl alcohol and methacrylic acid, 0.115 moles (9.90g) . Ωie mixture is refluxed for 1/2 hour to form a partial complex with the zirconium. A 94.9g portion of the aluminum chloride propylene glycol reaction product of Example 1 containing 0.197 moles Al, is then fed to the reactor vessel and the reaction completed during a reflux period of 1/2 hour following the completion of the feed. Infrared spectroscopy indicates the product thus prepared to be a hybrid complex wherein the methacrylic acid forms a complex bridge between the aluminum and zirconium metal centers. Methacrylic acid, like most carboxylic acids, is characterized by a strong band at 1700 απrl, representing the -C=0 functionality, and by a strong band at 1635 cπrl, representing the olefinic function, -C=C-. Upon complexation, the pi bond becomes delocalized over the 3 atom carboxy systan O-C-O, resulting in a weakened C=0 bond which is observed as a downfield shift of the carboxy band, and an upfield shift of the olefin band from 1635 cπrl to 1645 cπrl. It is noteworthy that upon conversion of methacrylic acid to the corresponding sodium salt the aforementioned shift of the olefinic absorbance at 1645 cπrl is accompanied by a pronounced reduction in absorption intensity which is not observed when a complex is formed. Hence, in the subject composition the product of Example 2 is observed to have complex bands at 1570 cπrl and 1595 cπrl, (Figure 4) and also a strong band at 1645 cπrl indicative of the formation of a true complex rather than a salt. The absence of a band at or around 1700 cπrl indicates that virtually all methacrylic acid is present in complex form. Reaction of methacrylic acid with sz . the zirconium OMPI ^ ATl oxychloride moiety (Figure 2) results in a zirconium methacrylate salt; a carboxy anion band at 1560 cπrl and an accompanying weak olefinic band at 1645 cπrl. n ϋke fashion, the reaction of the methacrylic acid with Q∑ . the complex aluminum moiety (Figure 3) results in a single band at 1595 cπrl. i is thus believed that the product composition is a hybrid structure having complex bands at 1570 cπrl and 1595 cπrl wherein the organofunctional group is chemically united to both aluminum and zirconium. The product thus prepared has the following characteristics: Specific Gravity (g/ml) 1.00, Flash Point (°F) 74, Decomposition Point (°C) > 300, Active matter (wt % solids) 17.5, pH (2% solution) 3.50, Aluminum (wt %) 2.95, Zirconium (wt %) 1.70. EXAMPLE 3: PREPARATION OF SEC-PROPANOLATO ALUMINUM CHLORO¬ HYDRATE SOLID Aluminum chlorohydrate, 0.197 moles Al (21.38g, 5/6 basic) is dissolved in an equal part of water. The solution is brought to reflux, whereupon a methanolic solution of propylene glycol, 0.0985 moles (7.49g) , is fed to the reactor and reflux maintained subsequent to the addition for 1/2 hour. The reaction product solution is placed in a drying oven at 110°C-120°C for one hour to remove solvent. The dried powder remaining is sec-propanolato aluminum chlorohydrate, 1/2 basicity. This product is equivalent to the product of Example 1 and thus, the IR spectrum for this product is comparable to the spectrum shown in Figure 1. EXAMPLE 4: PREPARATION OF CAREOXYIATO FUNCTIONAL ALUMINUM ZIRCONIUM ME33___D-ORGANIC COMPLEX Zirconium oxychloride powder, (44.8% Zr) 0.0329 moles Zr (6.85g) , is combined with 60.00g of isopropyl alcohol, 30.00g of acetone, and 4.00g of concentrated hydrochloride acid. An alcoholic solution of the reaction product of Example 1 is prepared by dissolving a 27.92g portion of sec-propanolato aluminum chlorohydrate, 0.197 moles Al in 35.00g of methanol. OMPI ^ Α > 18 The zirconium oxychloride solution as described is heated to 45°C-60°C whereupon the solution of sec-propanolato aluminum chlorohydrate is added. The mix formed thereby is heated to reflux and such temperature is maintained for one hour. Thereupon, 0.0823 moles (12.00g) of adipic acid is added and reflux continued until complexation is complete as determined by infrared spectroscopy (Figure 7) . The product thus prepared has the following characteristics: Specific Gravity (g/ml) 0.937, Flash Point (°F) 67, Decomposition Point (°C) >300, Active Matter (wt %) 22.7, pH (2% Solution) 3.80, Aluminum (wt %) 2.65, Zirconium (wt %) 1.55, Water (wt %) 1.28. Infrared spectroscopy indicates the product thus prepared to be a hybrid complex wherein one carboxy group of adipic acid forms a complex bridge between the aluminum and zirconium metal centers and the other carboxy group remains uncσmplexed. Adipic acid, like most carboxylic acids, is characterized by a strong band at 1700 cπrl representing the -0=0 functionality. Upon cσmplexation, the pi bond becomes delocalized over the 3 atom carboxy systan O-C-O resulting in a weakened C-O bond which is observed as a downfield shift. Hence, in the subject composition, (Figure 7) the product is observed to have complex bands at 1585 αιrl(sZ), 1610 crarl(s). Furthermore, one -C0OH of the dibasic acid remains uncoπplexed as indicated by the residual bands at 1700 cπrl and 1735 cπrl. Reaction of adipic acid with only the complex aluminum moiety (Figure 6) results in a spectrum having only one complex peak at 1615 cπrl (and free -C00H at 1695 cπrl) . m iik e fashion, reaction of the adipic acid with only the zirconium oxychloride moiety (Figure 5) results in a water insoluble product having complex peaks at 1540 cπrl and 1564 cπr- and loosely bound -C00H at 1735 cπrl. The -spectrum and related solubility properties suggest that the zirconium complex form may be a salt analogous to sodium adipate. It is thus believed that the product composition having complex peaks at 1585 cm~l and 1610 cm~l is a hybrid structure in which the bidentate organofunctional ligand is bound to both a zirconium and aluminum atom. By similar reasoning and spectral interpretation. Examples 5, 6, 7 are observed to have a comparable structure whereby the organofunctional ligand R2COO is bound to both a zirconium and aluminum atom. EXAMPLE 5: PREPARATION OF CARBOXYLATO FUNCTIONAL ALUMINUM (REDUCED BASICITY) ZIRCONIUM META1__ 0RGANIC COMPLEX Zirconium oxychloride powder, (44.8% Zr) 0.0376 moles Zr (7.79g) , is combined with 68.27g of isopropyl alcohol, 34.14g of acetone, and 4.55g of concentrated hydrochloric acid. An alcoholic solution of the reaction product of Example 3 is prepared by dissolving a 27.96g portion of the sec-propanolato aluminum chlorohydrate (1/2 basic) , 0.225 moles Al, in 28.63g of methanol. Subsequent to complete dissolution, concentrated hydrochloric acid, 11.10g, is slowly added to the reactor with agitation. The rate of addition is controlled so as to prevent the reaction exotherm from exceeding 50°C. The aluminum intermediate formed thereby is 1/3 basic. The zirconium oxychloride solution as described is heated to 45°C to 60°C whereupon the aforementioned reduced basicity (1/3 basic) sec-propanolato aluminum chlorohydrate solution is added. The reaction mixture is then heated to reflux and maintained at that temperature for one hour. Thereupon, adipic acid, 0.0935 moles (13.66g) is added and reflux continued until cσmplexation is coπplete as determined by infrared spectroscopy, as shown in Figure 8. Infrared spectroscopy indicates the product thus prepared to be a hybrid complex wherein one carboxy group of adipic acid forms a complex bridge between the aluminum and zirconium metal centers and the other carboxy group ranains umcomplexed. The product thus prepared has the following characteristics: Specific Gravity (g/ml) 0.974, Flash Point (°F) 67, Decomposition Point (°C) >300, Active Matter (wt %) 24.1, pH (2% Solution) 4.20, Aluminum (wt %) 2.65, Zirconium (wt %) 1.55 Water (wt %) 5.00. EXAMPLE 6: PREPARATION OF C12-C-18 FUNCTIONAL ALUMINUM ZIRr- CONIUM METALLO ORGANIC COMPLEX Zirconium oxychloride powder, (44.8% Zr) 0.0329 moles Zr (6.85g) , is combined with 60.00g of isopropyl alcohol, 30.00g of acetone, and 4.00g of concentrated hydrochloric acid. An alcoholic solution of the reaction product of Example 3 is prepared by dissolving a 27.92g portion of the sec-propanolato alurc num chlorohydrate, 0.197 moles Al, in 35.00g of methanol. The zirconium oxychloride solution as described is heated to 45°C-60°C whereupon the solution of sec-propanolato aluminum chlorohydrate is added. The mix formed thereby is heated to reflux and such temperature is maintained for one hour. Thereupon, a blend of fatty acids, consisting of 90% C14, 10% C12 and C±ζ, of 0.0822 moles (18.74g) , is added and reflux continued until complexation is at least 70% complete as determined by infrared spectroscopy (Figure 9) . Infrared spectroscopy indicates the product thus prepared to be composed of 70% of a hybrid coπplex wherein the fatty acids form a complex bridge between the aluminum and zirconium metal centers and the remaining 30% is weakly complexed (1740 cπrl). The product thus prepared has the following characteristics: Specific Gravity (g/ml) 0.923, Flash Point (°F) 67, Decomposition Point (°C) >300, Active Matter (wt %) 25.7, pH (2% Solution) 4.50, uminum (wt %) 2.65, Zirconium (wt %) 1.55, Water (wt %) 1.28. EXAMPLE 7: PREPARATION OF CT2 - CTR, METHACRYLATO MIXED FUNCTIONAL ALUMINUM ZiffiCONIUM MES3ALL0-ORGANIC COMPLEX Zirconium oxychloride powder, (44.8% Zr) 0.0329 moles Zr OMPI 21 (6.85g) , is combined with 60.00g of isopropyl alcohol, 30.00g of acetone, and 4.00g of concentrated hydrochloric acid. Methacrylic acid, 0.0655 moles (5.64g), is added to the mixture with agitation at ambient temperature. The mixture is heated to reflux temperature and held for 0.5 to 1.0 hours. An alcoholic solution of the reaction product of Example 3 is prepared by dissolving sec-propanolato aluminum chlorohydrate, 0.197 moles Al (27.92g) in 50.00g of ethanol. The reaction mixture described above is cooled to 45°C whereupon the solution of sec-propanolato aluminum chlorohydrate is added. The resultant aluminum zirconium methacrylato mixture is reheated to reflux for 0.5 to 1.5 hours. The aluminum zirconium methacrylato product is cooled to 60°C whereupon a blend of fatty acids, consisting of 90% C14, 10% C12 and Ci6, 0.0822 moles (18.74g) , is added and reflux continued until complexation is at least 70% complete as determined by infrared spectroscopy (Figure 10) . Infrared spectroscopy indicates the product thus prepared to be a compound of a hybrid complex wherein the 70% of the fatty acids and 100% of the methacrylic acid form a coπplex bridge between aluminum and zirconium metal centers. The product thus prepared has the following characteristics: Specific Gravity (g/ml) 0.910, Flash Point (°F) 67, Decomposition Point (°C) > 300, Active Matter (wt %) 24.0, pH (2% Solution) 3.70, Aluminum (wt %) 2.63, Zirconium (wt %) 1.51, Water (wt %) 1.26. EXAMPLE 8: TREATMENT OF INORGANIC MINERAL FILLERS WITH ALU¬ MINUM Z-ffiCONIUM M__!AI_£ >RGANIC SURFACE MODIFIERS This example teaches the use of compositions of this invention for the surface modification of finely divided inorganic mineral fillers characterized by particle sizes between 0.5 and 5.0 microns. Thus, filler dispersions were prepared as shown in the accompanying table at the indicated concentrations and in the indicated solvents. For example, 400g of alumina trihydrate (1 micron particle size) is dispersed in 600g of deionized water using a 4 blade high speed paint agitator. To a 150g sample of the dispersion containing 60g of alumina trihydrate having a viscosity of 19800 cps (Brookfield. Spindle 5, 20rpm) is added 0.9g (1.5 phf) of the coπposition of Example 5 (0.34 phf of active matter) . ~~ e slurry is agitated manually for 30 seconds at 20°C whereupon the viscosity is determined to have decreased to 500 cps (Brookfield. Spindle 5, 20 rpm). Seven days later the viscosity of the treated slurry has undergone further viscosity reduction to <50 cps, hence suggestive of the irreversibility of surface modification (Table I). Alternatively, the composition of Example 7, 0.9g (1.5 phf, 0.34 phf of active matter) may be dissolved in 90g of deionized water. Alumina trihydrate, 60g, is added to the aqueous mix whereupon a slurry having a viscosity of 100 cps results (Brookfield. Spindle 5, 20 rpm). It is abundantly documented (Table I) that surface modification of the indicated mineral fillers with the compositions of Examples 2, 3, 4, 5, 6, 7, 12(e) result in pronounced and irreversible reductions in filler slurry viscosity in excess of 98 percent. It is further noted that the addition sequence by which a slurry is prepared can markedly affect the observed viscosity. Such is the case with calcium carbonate in alcohol where addition to the slurry is marginally effective (17.5% viscosity reduction after 7 days) as contrasted with prior dissolution of the surface modifier in solvent which results in >99% reduction in viscosity. Examination of the data pertaining to Tiθ2 (Table I) is indicative of the preferred use of a specific coπposition with a given filler due to significant differences in surface modifier performance. TABLE 3 Al-Zr Al-Zr SURFACE SURFACE VISCOSITY, cps SLURRY MODIFIER MODIFIER C0NC phf, ACTIVE EXAMPLE ADD'N INITIAL 7 DAY FILLER flπrVFN T % MATTER NUMBER MODE U/T TREATED TREATED Alumina Water 40 0.20 2 Slurry 2 20,000 100 <100 Trihydrate Solvent 12,700 500 500 (1 micron) Water 40 0:34 5 Slurry 19,800 500 <50 Solvent 12,500 100 100 Alcohol 40 0.20 2 Slurry 20,000 <100 <100 Alcohol 40 0.23 7 Slurry 20,000 <100 <100 Calcium Alcohol 70 0.30 2 Slurry 50,000+ 34,000 19,500 Carbonate Solvent 50,000+ 500 250 (1 micron) Alcohol 70 0.34 5 Slurry 20,000 34,000 16,500 Solvent 39,280 500 250 Silica Water 70 0.35 2 Slurry 12,000 5,500 2,750 (1.8 micron) Water 70 0.46 7 Slurry 16,000 <100 Alcohol 70 0.03 2 Slurry 13,200 300 400 Solvent 2,100 200 200 Alcohol 70 0.03 4 Slurry 49,000 200 100 Solvent 26,250 200 100 Clay Alcohol 70 0.3.0 12(e) Slurry 20,500 750 3,500 (4 micron) 12(e) Solvent 21,000 250 2,250 Surface modifier added to filler slurry. "Surface modifier dispersed in solvent, filler added. TABLE I - Continued . Al-Zr Al-Zr SURFACE SURFACE VISCOSITY, cps SLURRY MODIFIER MODIFIER CONC phf, ACTIVE EXAMPLE ADD'N INITIAL 7 DAY FILLER SOLVENT T % MATTER NUMBER MODE U/T TREATED TREATED Clay Alcohol 60 0.34 4 Slurry 16,000 2,000 250 (4 micron) Solvent 18,250 <50 250 Titanium Water 70 0.10 2 Slurry 49,000 750 500 Dioxide Solvent 50,000+ 750 500 (0.5 micron) Water 70 0.24 ' 7 Slurry 50,000+ • 750 500 0.30 Solvent 50,000+ 1,000 850 Water 70 0.24 4 Slurry 50,000+ 500 1,500 Alcohol 0.10 2 Slurry 50,000 9,250 1,000 Alcohol 70 0.24 4 Slurry 50,000 250 <100 t EXAMPLES 9 - 27: OTHER ALUMINUM/ZIRCONIUM METALLO- ORGANIC AGENTS In a manner similar to that detailed for Examples 1 through 7, other aluminum zirconium metallo-organic complex agents were prepared having the substituents and ratios of substituents. indicated in Table II below. Basicitv of Example -OR-iO- ___£__! ___ Y: (2X+Z) Al2≤bE 9 - CH(CH3) <__2-O- CH2*=C(CH3) COOH 1.5:1 .25 0.5 10 π n 2:1 .36 0.5 11 π n 3:1 .36 0.5 2(a) It It It It 4.5:1 .13 0.5 IS n π 4.5:1 .53 0.5 π It 4.5:1 .31 0.5 IS If π 4.5:1 .36 0.5 4.5:1 .24 0.5 3 π It 6:1 .36 0.5 4 n π 7.5:1 .36 0.5 5 π CH2=CH-C00H 3:1 .36 0.42 6(a) It H2-CHgCH2C0(X3 4.5:1 .13 0.5 (b) It .25 0.5 (c t π 4. ) I 5:1 4.5:1 .50 0.5 8(a) It BOCC CH2C00H 3:1 .36 0.33 (b) π (c) π It 3:1 .36 0.42 3:1 .36 0.50 9(a) n π H00C(CH2) 2GOOH 3:1 .36 0.33 (b) .42 (c) π It 3:1 .36 0 3:1 .36 0.50 0(a) It (b) π HOOC(CH π2) 3OOOH 3:1 .36 0.33 (c) n π 3:1 .36 0.42 3:1 .36 0.50 1(a) π OCH 3:1 .36 0.33 (b) π HOOC(CH2) 4C (c) π π 3:1 .36 0.42 3:1 .36 0.50 2 π H00C(CH2) 4CCOH 3:1 .50 0.42 3 H CH2=CCCH3)COCB 4.5:1 .50 0.67 4 It CH2=C(CH3)OOOH 3:1 .50 0.67 OMPI 26 Example ._____ £ ∑2£_Q_ ___ Yi (2X+Z? _ L2&bBc 25 -OCH(CH3)CH2-0- CH2=C(CH3)C00H 1.5:1 .50 0.67 26(a) -0-CH2^ O- CH2=C(CH3)C0(B 3:1 .50 0.5 (b) • _> • X .50 0.33 27 " CH2=C(C_3)C00H 4.5:1 .50 0.5 All of the compositions provide aluminum zirconium metallo-organic treatment agents which were useful in improving the surface properties of inorganic fillers and like materials. It is also possible to obtain useful compositions using other organic reactants and other Al:Zr ratios and basicities, outside the range indicated in Table II, but such products should be checked for stability and effectiveness before use. Preferably, the compositions made in accordance with the present invention have shelf life of at least 30 days. EXAMPLE 28: PREPARATION AND USE OF INORGANIC MINERAL FILLER PRETREATED WITH ALUMINUM ZIRCONIUM METALLO-ORGANIC SURFACE MODIFIERS A 70 wt % alcoholic dispersion of silica (1.8 micron praticle size) is prepared as per the procedure described in Exaπple 8. To the slurry is added 0.03 phf (active matter) of an aluminum zirconium metallo-organic surface modifying agent, made in accordance with the procedure of Exaπple 4 having the composition of Exaπple 21(c). The viscosity of the untreated and treated slurry is noted (as shown in Table III) . The slurry is then placed in a drying oven at 110°C for 30 minutes to remove solvent whereupon to the dry treated silica is added an amount of alcohol equivalent to that which is removed during the drying process. The silica is redispersed and the viscosity is measured and observed to be equivalent to the analogous slurry prior to drying. The results are shown in Table III. OMPI 27 TABLE III Al-Zr SURFACE PROCESS MODIFIER VISCOSITY DESCRIPTION SOLVENT phf.ACTIVE MATTER cps 1. Untreated Silica Alcohol 9000 Slurry 2. Treated Silica Alcohol 0.03 <100 Slurry 3. Dry Silica Alcohol 4. Redispersed Alcohol <100 Treated Silica Similarly, a 40 wt % alcoholic dispersion of alumina trihydrate (1 micron particle size) is prepared, treated with 0.34 phf (active matter) of an aluminum zirconium metallo-organic surface modifier and then processed as described in the foregoing silica dispersion system. The results (Table IV) show a 90% viscosity reduction upon adding the surface modifier and >99.5% viscosity reduction upon drying and redispersion. TABLE IV Al-Zr SURFACE PROCESS MODIFIER VISCOSITY PESCRIPTION. SOLVENT ph ,ACTIVE MATTER CBS 1. Untreated Alumina Alcohol 50000+ Trihydrate Slurry 2. Treated Mumina Alcohol 0.34 5000 Trihydrate Slurry 3. Dry Alumina Trihydrate - 4. Redi;_. rsed Alumina Trihy ate Alcohol 0.34 <100 EXAMPLE 29: PHYSICAL PROPERTIES OF FIBERGLASS REINFORCED POLYESTER LAMINATES Fiberglass was prepared and treated with an aqueous size bath containing aluminum zirconium metallo-organic coupling agent. Subsequently, fiberglass reinforced polyester laminates were prepared using a United States Steel general purpose unsaturated orthophthalic polyester resin (approx. 70%) and the treated fiberglass (approx. 30%) . Ttøo similar fabricated laminates were prepared using commercially available methacrylato chromic chloride and methacrylato silane under identical conditions. The laminates were then evaluated for wet and dry physical properties. The results (Table V) clearly show that the aluminum zirconium metallo-organics of this invention impart excellent dry strength (tensile, flexural) to such laminates and, more importantly, provide protection from hydrolytic interfacial degradation which is most readily reflected in the percentage of retention for both tensile and flexural strength. The aluminum zirconium metallo-organics are observed to exhibit performance comparable to the methacrylato silane and exceeding the methacrylato chromic chloride. In this Example, Al-Zr coupling agents 1, 2 and 3 are compositions corresponding to Examples 12(a), 12(b) and 12(c), respectively. OMPI TABLE V MEΠΉACRYLATO Al-Zr Al-Zr Al-Zr CHROMIC CHLORIDE METHACRYLATO COUPLING COUPLING COUPLING COS1TROL SILANE AGENT 1 AGENT 2 AGENT 3 Tensile (Dry) psi 10,900 9,850 13,700 12,000 9,700 (Wet). 9,300 8,920 9,100 10,500 10,700 % Retentionl 85.5 90.6 66.2 87.8 110 Flexural Strength (Dry) psi 25,400 21,780 26,700 24,400 23,200 (Wet) 17,700 18,660 17,800 18,100 19,000 % Retentionl 70.0 85.7 66.8 74.0 85.2 Flexural Modulus (Dry) 9.14xl0 5 7.4xlθ| 8.52xl0 5 8.14xlOJ? 9.20xl0 5 (Wet) 5.86xl0 5 6.4xl0 5 5.68xl0 5 5.94xl0 5 6.75xl0 5 % Retention 1 64.0 86.7 66.7 73.0 73.4 Notched Izod (Dry) 11.8 14.5 13.7 10.3 10.1 (Wfet) 12.0 14.1 11.6 11.7 12.3 % Retentionl 102 97.3 84.7 114 123 Wet Strength rs n o lng y water . . :, 30 * EXAMPLE 30: SURFACE TREATMENT OF PAPER SUBSTRATES TO IMPART DURABLE WATER REPELLANCY A 5 wt % aqueous bath of the product of Example 6 is prepared. A 3"x6 π section of unbleached kraft paper is saturated in the solution, padded, and dried at 100°C for 2 minutes. Similarly, two 3 π x6" sections of unbleached kraft paper are saturated in 5% solutions of DuPont Quilon C and L (a commercially used water repellant) , padded, and dried at 110°C for 2 minutes. One drop of deionized water is carefully placed on the flattened surface of each of the above sheets and also on the untreated kraft stock. In the latter instance, the water is observed to penetrate upon contact. In contrast, after 24 h. there is no indication of surface wetting on the sheets treated with either the aluminum zirconium metallo-organic or the Quilon C or L. Additionally, whereas the Quilon products impart a distinctly green color to the substrate, treatment with the aluminum zirconium metallo-organic results in no apparent discoloration. In like fashion, textile substrates may be treated with the composition of Exaπple 6 achieving similar water repellancy without undesirable iπpact on aesthetics. While the exemplary embodiments have been disclosed with particularity, other embodiments will be readily apparent to those skilled in the art frcm consideration of the present disclosure, or from practice of the invention diclosed herein. The embodiments discussed are to be considered as exemplary only, and the true scope of the invention should be determined by a consideration of the appended claims.

Claims: Claims 1. A composition of matter comprising the reaction product of a chelated aluminum moiety, an organofunctional ligand and a zirconium oxyhalide, the aluminum moiety having the formula: Al2 ( ORiO ) aAbBc wherein A or B is hydroxy or halogen and a, b and c are numerical values such that 2a + b + c = 6, and -ORiO- is (a) an alpha, beta or alpha, gamma glycol group in which Ri is an alkyl, alkenyl or al yπyl group having 1 to 6 carbon atoms or (b) an alpha-hydroxy carboxylic acid residue having the formula: R30 I H -O-CH-C-O- wherein R3 is H or an alkyl group having frcm 1 to 4 carbon atαns; the organofunctional ligand is (1) an alkyl, alkenyl, alkynyl or aralkyl carboxylic acid having frcm 2 to 36 carbon atoms, (2) an aminofunctional carboxylic acid having frcm 2 to 18 carbon atoms, (3) a dibasic carboxylic acid having frcm 2 to 18 carbon atoms, (4) an acid anhydride of a dibasic acid having frcm 2 to 18 carbon atoms, (5) a mercapto functional carboxylic acid having frcm 2 to 18 carbon atoms, or (6) an epoxy functional carboxylic acid having from 2 to 18 carbon atoms; and the zirconium oxyhalide moiety has the formula: ZrAdBe wherein A and B are as above-defined and d and e are numerical values such that d + e = 4; the molar ratio of chelated aluminum moiety to zirconium oxyhalide moiety being from about 1.5 to 10, 32 and the molar ratio of organofunctional ligand to total metal being from about 0.05 to 2. 2. The coπposition of matter of claim 1, wherein said composition is soluble in alcohols, ketones, carboxylic acids, carboxylic acid esters, tetrahydrofurane, dioxane, dimethylformamide dimethylsulfone, di ethylacetamide, a halogenated hydrocarbon, mineral oil, xylene or toluene. 3. The composition of claim 1, wherein Ri is an alkyl group of 2 or 3 carbon atoms or -(R3)CH-O0- and R3 is H or CH3. 4. he coπposition of claim 1, wherein the reaction product corresponds to the empirical formula: EA12<PRχO ) aAbBc3χ ICC ( R_ ) 0]Y[Zr dB e 3Z and the ratio of X:Z is from about 2:1 to about 5:1. 5. The composition of claim 4, wherein the ratio of Y:2X+Z is from about 0.1 to about 1.0. 6. Ωie composition of claim 4, wherein Ri is alkyl of 2 or 3 carton atoms or -(IQ)CH-C=0-, R3 is H or alkyl of 1 to 4 carbon atoms and 2 is alkenyl of 2 to 5 carbon atoms, aminoalkyl of 1 to 5 carbon atoms or an alkyl carboxylic acid having 1 to 18 carbon atoms. 7. The coπposition of claim A, wherein Ri is alpha, beta propyl or methyl acyl and R.2 is 2-methyl propenoic acid, propenoic acid, beta alanine, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, or a fatty acid. 8. The composition of claim 4, wherein X:Z is about 3:1, Y: ( X+Z)is about 0.5, A is hydroxy, B is chlorine, R.χ is n-propyl or isopropyl, R2- is πethacrylic acid, a is about 0.25, b is about 2.5, and c is about 3. 9. The coπposition of claim 4, wherein X:Z is about 4.5:1, Y:(2X+Z) is about 0.5, A is hydroxy, B is chlorine, Ri has three carbon atoms, R2COO- is beta alanine, a is about 1, b is about 3, and c is about 1. -% LχTE ~ OMPI YΛ,^ IPO _ _-.-• ■• 33 10. The coπposition of claim 4, wherein X:Z is about 3:1, Y:(2X+Z) to about 0.35, A is hydroxy, B is chlorine, Ri has 3 carbon atoms, R2COO- is adipic acid, a is about 0.25, b is about 2.5, and c is about 3.00. 11. The composition of claim 4, wherein X:Z is about 3:1, Y:(2X+Z) is 0.5, A is hydroxy, B is chlorine, Ri is n-propyl or isopropyl, R2COO- is methacrylic acid, a is about 1, b is about 3, c is about 1. 12. The composition of claim 4, wherein X:Z is about 3:1, Y:(2X+Z) is about 0.35, A is hydroxy, B is chlorine, Ri has 3 carbon atoms R2COO- is adipic acid, a is about 1, b is about 3, and c is about 1. 13. he coπposition of claim 4, wherein X:Z is about 3:1, Y:(2X+Z) is about 0.35, A is hydroxy, B is chlorine, Ri has 3 carbon atoms, R2COO- is adipic acid, a is about 1, b is about 2, and c is about 2. 14. The composition of claim 4, wherein X:Z is about 3:1, Y:(2X+Z) is 0.50, A is hydroxy, B is chlorine, Ri has 3 carbon atoms, R2COO- consists of a combination of 2-methyl-propenoic acid and C12, C14 and Cχ6 fatty acids, a is about 1, b is about 3, and c is about 1. 15. The composition of claim 4, wherein X:Z is about 3:1, Y:(2X+Z) is about 0.35, A is hydroxy, B is chlorine, Ri is n-propyl, isopropyl, R2CO- is myristic, palmitic, stearic, or oleic acid, or mixtures thereof. 16. The composition of claim 15, wherein R2CO - is a mixture of fatty acids containing about 90% πyristic acid. 17. A method of preparing a composition useful as a coupling agent, comprising reacting a chelated aluminum moiety with an organofunctional ligand and a zirconium oxyhalide, the aluminum moiety having the formula: Al2 ( ORiO ) a AbB C <*- τ llEJVζ OMPI fym wipo wherein A or B is hydroxy or halogen and a, b and c are numerical values such that 2a + b + c = 6, and -ORiO- is (a) an alpha, beta or alpha, gamma glycol group in which R is an alkyl, alkenyl or alkynyl group having 1 to 6 carbon atoms or (b) an alpha-bydroxy carboxylic acid residue having the formula: R30 I II -O-CH-C- - wherein ΕQ is H or any alkyl group having from 1 to 4 carbon atoms; the organofunctional ligand is (1) an alkyl, alkenyl, alkynyl or aralkyl carboxylic acid having from 2 to 36 carton atoms, (2) an aminofunctional carboxylic acid having from 2 to 18 carbon atoms, (3) a dibasic carboxylic acid having from 2 to 18 carbon atoms, (4) an acid anhydride of a dibasic acid having frcm 2 to 18 carbon atoms, (5) a mercapto functional carboxylic acid having frcm 2 to 18 carbon atoms, or (6) an epoxy functional carboxylic acid having frcm 2 to 18 carbon atoms? and the zirconium oxyhalide moiety has the formula: ZrA<_Be wherein A and B are as above-defined and d and e are numerical values such that d + e = 4? the molar ratio of chelated aluminum moiety to zirconium oxyhalide moiety being from about 1.5 to 10, and the molar ratio of organofunctional ligand to total metal being from about 0.05 to 2. 18. The method of claim 17, wherein the reaction is carried out in a solvent comprising water, alkyl alcohol having frcm 1 to 12 carbon atoms, an alkyl ketone having from 1 to 6 carbon atoms, or mixtures thereof. 19. The method of claim 18, wherein Ri is alkyl of 2 or 3 carbon atoms or -(R3)CH-G=0-, and R3 is H or CH3. OMPI 20. The method of claim 18, wherein the reaction product corresponds to the empirical formula: EA12 ( ORiO ) st b crx ( OC ( 2 ) 0]y[ZrAdBe]z and the ratio of X:Z is from about 2:1 to about 5:1. 21. The method of claim 18, wherein the ratio of Y: (2X+Z) is from about 0.1 to about 1.0, Ri is alkyl of 2 or 3 carbon atoms or -(R3)CH-C=0-, R3 is H or alkyl of 1 to 4 carbon atoms, and R2 is 2-methyl propenoic acid, propenoic acid, beta-alanine, oxalic acid, malonic acid, succinic acid, glutaric acid or adipic acid. 22. The method of claim 18, further comprising forming the aluminum halohydrate chelate complex by reacting an aluminum halohydrate with a bidentate chelating agent having the formula HORiOH, wherein _ is an alkyl, alkenyl or alkynyl group having frcm 1 to 6 carbon atoms, or -(R3)CH-C=0-, where R3 is H or an alkyl group having from 1 to 4 carbon atoms. 23. The method of claim 22, where the aluminum halohydrate is aluminum chlorohydrate, having a basicity of from 0 to 0.83. 24. The method of claim 22, wherein the reaction between the aluminum halohydrate and the bidentate chelating agent is conducted in a solvent selected frcm water, alkyl alcohols having from 1 to 12 carbon atoms and ketones having frcm 1 to 6 carbon atoms, and mixtures thereof. 25. The method of claim 22, where the chelated aluminum moiety, organofunctional ligand and zirconium oxyhalide are reacted in a solvent which is a mixture of an alkyl alcohol having frcm 1 to 3 carbon atoms, and an alkyl ketone having from 1 to 3 carbon atoms, the final concentration of coupling agent in the solvent being frcm about 15 to 50 percent. 26. A composition of matter comprising the product of admixture of? (I) the reaction product of a chelated aluminum moiety, an organofunctional ligand and a zirconium oxyhalide, the fREAcT OMPI - • - _ 36 aluminum moiety having the formula: Al2 ( ORLO ) a AbBc wherein A or B can be hydroxy or halogen and a, b and c are numerical values such that 2a + b + c = 6, and -ORiO- is (a) an alpha, beta or alpha, gamma glycol group in which Ri is an alkyl, alkenyl or alkynyl group having 1 to 6 carbon atoms or (b) an alpha-bydroxy carboxylic acid residue having the formula: R3 O II ■ H0-CH-C- - wherein S3 is H or an alkyl group having frcm 1 to 4 carbon atoms; the organofunctional ligand is (1) an alkyl, alkenyl, alkynyl or aralkyl carboxylic acid having from 2 to 36 carbon atoms, (2) an aminofunctional carboxylic acid having frcm 2 to 18 carbon atoms, (3) a dibasic carboxylic acid having from 2 to 18 carbon atoms, (4) an acid anhydride of a dibasic acid having from 2 to 18 carbon atoms, (5) a mercapto functional carboxylic acid having from 2 to 18 carbon atoms, or (6) an epoxy functional carboxylic acid having from 2 to 18 carbon atoms; and the zirconium oxyhalide moiety has the formula: ZrAdBe wherein A and B are as above-def ned and d and e are numerical values such that d + e = 4; the molar ratio of chelated aluminum moiety to zirconium oxyhalide moiety being frcm about 1.5 to 10, and the molar ratio of organofunctional ligand to total metal being from about 0.05 to 2, and (II) a substrate, said substrate being: (a) filler selected from the group of glass, silica, calcium carbonate, alumina trihydrate, aluminum silicate. -^ lE_A OMPI talc, wollastonite, mica, titanium dioxide, and an organic particulate having reactive groups; (b) paper; (c) fiberboard; (d) textile; or (e) mixture thereof. 27. The coπposition of claim 26, wherein the substrate filler comprises glass. 28. The composition of claim 27, wherein the glass filler comprises glass fibers. 29. A composite product, comprising the composition of claim 26 and a resin selected frcm the group of thermoset, thermoplastic and elastomeric resins.

Inventors: COHEN LAWRENCE B, COHEN, LAWRENCE, B.
Applicants: CAVEDON CHEM CO INC, CAVEDON CHEMICAL COMPANY, INCORPORATED
Application year: 1984
Main classification: C07F7
IPC codes: C07F7