USOO7250.46OB1

(12) United States Patent (10) Patent No.: US 7.250.460 B1 Takamura (45) Date of Patent: *Jul. 31, 2007

(54) INORGANIC-ORGANIC POLYMER 3,951,676 A 4, 1976 Elste, Jr. NANOCOMPOSITE AND METHODS FOR 3,959,204 A 5/1976 Dunn ...... 524/425 MAKING AND USING 4,251,416 A 2, 1981 Palmer ...... 524/423 4,296,207 A 10/1981 Siegmund (75)75 Inventor: KoichiO O Takamura, Charlotte, NC (US) 4.462,8404,456,534. A * 7/19846/1984 SchillingLambert etet al.al...... 21Of 725 4,597,799 A 7/1986 Schilling (73) Assignee: BASF AG, Ludwigshafen 4,772,648 A 9/1988 Demangeon et al. Rheinland-Pfalz (DE) 4,921,892. A 5/1990 Moore et al. c - 0 4.944,804. A 7/1990 Schilling (*) Notice: Subject to any disclaimer, the term of this 5,160,453 A 1 1/1992 Schilling patent is extended or adjusted under 35 5,268,029 A 12/1993 Demangeon et al. U.S.C. 154(b) by 287 days. 5,443,632 A 8/1995 Schilling 5,667,718 A 9, 1997 Jones et al. This patent is Subject to a terminal dis- 5,843.222 A 12/1998 Miller et al. claimer. 6,000,876. A 12/1999 Shen et al. (21) Appl. No.: 10/828,457 FOREIGN PATENT DOCUMENTS GB 2151 640 7, 1985 (22) Filed: Apr. 20, 2004 RU 2O71491 * 1/1997 WO WO O2/O24759 3, 2002 Related U.S. Application Data WO WOO3,OOOT60 1, 2003 (63) Continuation-in-part of application No. 10/332,894, filed as application No. PCT/US02/33343 on Jun. 18, OTHER PUBLICATIONS 2002, now Pat. No. 6,855,754, application No. English Copy of International Search Report for PCT/US 02/33343 10/828,457, which is a continuation-in-part of appli- filed Jun. 18, 2002. cation No. PCT/US01/44988, filed on Nov. 20, 2001, Takamura, Koichi, SBR Syntheic Latex in Paving Application, which is a continuation of application No. 09/790, Bitumen Asia 2000, June 20-21, Singapore. 273 filed on Feb. 21, 2001. Brown, SF. A Study of Cement Modified Bitumen Emulsion s s Mixtures, pp. 92-121 Mar. 15, 2000. (60) Provisional application No. 60/256,709, filed on Dec. Wyoming Department of Transportation, Special Provision for 18, 2000. Micro Surfacing, Nov. 18, 1998. (51) Int. Cl. k cited. by examiner C08K 3/16 (2006.01) Primary Examiner Peter Szekely CSK 3/28 (2006.01) CSK 3/30 (2006.01) (57) ABSTRACT (52) U.S. Cl...... 524/423: 524/429; 524/80 (58) Field of Classification Search ...... 524/405, A method of forming a composition comprising adding at 524/417,423 424, 429, 394, 456, 80 least one first compound that is at least one of an alkali metal See application file for complete search history. salt, an salt, an alkali metal hydroxide, or an (56) References Cited ammonium hydroxide and at least one second compound that is at least one of a Group IIA salt, a Group IIIA salt, a U.S. PATENT DOCUMENTS Group IIIB salt, a copper salt, a Zinc salt, a cadmium salt, a manganese salt, an iron salt, a cobalt salt, or a nickel salt to 3,220,953. A 11/1965 Borgfeldt et al. 3,236,671 A 2/1966 Dybalaski et al. a latex. This method allows for the formation of nanopar 3,466,247 A 9, 1969 Ohtsuka et al. ticles in the composition. 3,660,324. A 5, 1972 Ohtsuka et al. 3,695,152 A 10, 1972 Graf 10 Claims, 6 Drawing Sheets U.S. Patent Jul. 31, 2007 Sheet 1 of 6 US 7.250.460 B1

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edw"ufueuS eSue US 7,250,460 B1 1. 2 NORGANIC-ORGANIC POLYMER phosphate nano-crystals. The latex films were heat treated at NANOCOMPOSITE AND METHODS FOR 100° C. for 3 hours after drying in ambient temperature for MAKING AND USING 6 days. FIGS. 6 (a) and (b) are graphs of tensile strength vs. CROSS-REFERENCE TO RELATED elongation for the latex films heat aged for 20 minutes (a) APPLICATIONS and 40 minutes (b) in a forced airflow oven at 160° C. FIG. 7 is a graph of tensile strength vs. elongation with This application is a continuation-in-part of U.S. Ser. No. BUTONAL(R) NS198 latex and Ca-phosphate nano-crystal 10/332,894, filed 14 Jan. 2003, which is a national stage modified latex. application of 10 A. International Application No. PCT/US02/33343, which DETAILED DESCRIPTION was filed on 18 Jun. 2002, which is a continuation-in-part of International Application No. PCT/US01/44988, which As used throughout, ranges are used as a shorthand for was filed on 20 Nov. 2001 (Nov. 20, 2001), which claims describing each and every value that is within the range. Any priority to U.S. Ser. No. 09/790,273, filed on 21 Feb. 2001 15 value within the range can be selected as the terminus of the (Feb. 21, 2001), and to U.S. Ser. No. 60/256,709, filed on range. When used, the phrase “at least one of refers to the 18 Dec. 2000 (Dec. 18, 2000), and selection of any one member individually or any combina tion of the members. The conjunction “and” or “or' can be B. International Application No. PCT/US01/44988, which used in the list of members, but the “at least one of phrase was filed on 20 Nov. 2001 (Nov. 20, 2001), which claims is the controlling language. For example, at least one of A, priority to U.S. Ser. No. 09/790,273, filed on 21 Feb. 2001 B, and C is shorthand for A alone, B alone, C alone, A and (Feb. 21, 2001), and to U.S. Ser. No. 60/256,709, filed on B, B and C, A and C, or A and B and C. 18 Dec. 2000 (Dec. 18, 2000), In the following detailed description, preferred embodi all of which are incorporated herein by reference. ments are described in detail to enable practice of the 25 invention. Although the invention is described with refer BACKGROUND OF THE INVENTION ence to these specific preferred embodiments, it will be understood that the invention is not limited to these pre Inorganic particles and/or clays have typically been incor ferred embodiments. But to the contrary, the invention porated into polymeric compositions during the polymer includes numerous alternatives, modifications and equiva ization of the polymer. This forms a nanocomposite com 30 lents as will become apparent from consideration of the position. This method may be difficult to accomplish. It following detailed description. would be desirable to have a method of forming nanocom The present invention includes a composition formed by posite compositions without the difficulty of addition of the mixing a polymer latex, at least one first compound selected nanoparticles during polymerization. from the group consisting of alkali metal salts, ammonium 35 salts, alkali metal hydroxides, and ammonium hydroxide; SUMMARY OF THE INVENTION and at least one second compound preferably selected from the group consisting of Group IIA, Group IIIA, Group IIIB, The invention relates to a method of forming a compo copper, Zinc, cadmium, manganese, iron, cobalt and nickel sition comprising adding at least one first compound that is salts. By combining alkali metal or ammonium salts or at least one of an alkali metal salt, an ammonium salt, an 40 hydroxides in Solution, and one or more salts such as a alkali metal hydroxide, or an ammonium hydroxide and at Group IIA, Group IIIA, Group IIIB, copper, zinc, cadmium, least one second compound that is at least one of a Group IIA manganese, iron, cobalt or nickel salts in solution, a com salt, a Group IIIA salt, a Group IIIB salt, a copper salt, a Zinc position is formed that contains fine inorganic crystals. salt, a cadmium salt, a manganese salt, an iron salt, a cobalt When the latex is dried, a latex polymer nanocomposite is salt, or a nickel salt to a latex. 45 formed. The polymer nanocomposite has improved mechanical and heat aging properties as compared to the BRIEF DESCRIPTION OF THE DRAWINGS polymer without the inorganic particles. The latex can be any latex. The latex is prepared before FIG. 1 is a photo-micrograph of fine inorganic crystals the addition of the first or second compound. Suitable generated by mixing equal volume of 30% aqueous CaCl2 50 polymer latices include, but are not limited to, cationic SBR and 35% (NH4)HPO solutions. (styrene-butadiene rubber) latices, natural rubber latices, FIG. 2 is a photo-micrograph of a thin cross-section of polychloroprene latices (e.g. NEOPRENER) latices avail dried latex film containing approximately 2 wt % of Ca able from E.I. Du Pont de Nemours), carboxylated (poly phosphate nano-crystals. styrene-butadiene) latices, and acrylic latices. The list of 55 various latices can be found in “Polymer Dispersions and FIG. 3(a) is a graph of the tensile strength vs. elongation Their Industrial Applications' ed. by D. Urban and K. of BUTONAL(R) NX1118 latex film with and without Ca Takamura, Wiley-VCH, 2002. These latices used for this phosphate nano-crystals. The latex was dried one day in invention should maintain their dispersion stability during room temperature then placed in an oven of 60° C. for the process. Preferably, a cationic SBR latex is used. The additional 24 hours. FIG. 3(b) is a graph of the tensile 60 cationic SBR latex emulsion typically includes between strength of the same films after being immersed in water for about 0.1 and about 10%, and more preferably, between 24 hours. about 2% and about 6% by weight cationic surfactants. The FIG. 4 is a graph of tensile strength vs. elongation similar latex used for this invention should remain as a stable to FIG. 3, but BUTONAL(R) NS198 latex was used instead dispersion by the addition of aqueous solutions of the second of the BUTONAL(R) NX1118 latex. 65 compounds. Suitable cationic SBR latices include FIG. 5 is a graph of tensile strength vs elongation for the BUTONAL(R) NX1118 and BUTONAL(R) NS 198, commer BUTONAL(R) NX1118 latex film with and without Ca cially available from BASF Corporation. US 7,250,460 B1 3 4 The present composition is prepared by mixing at least Group IIIB, copper, Zinc, cadmium, manganese, iron, cobalt one compound selected from the group consisting of alkali and nickel salts preferably used in the invention as discussed metal salts, alkali metal hydroxides, ammonium salts, and below. Preferably, the alkali metal and ammonium salts and ammonium hydroxide in the composition. The alkali metal hydroxides are provided in stoichiometric excess with and ammonium salts and hydroxides are preferably added to respect to these Group IIA, Group IIIA, Group IIIB, copper, the composition in aqueous solution in an amount from Zinc, cadmium, manganese, iron, cobalt and nickel salts. In greater than 0 to about 4 parts by weight, more preferably, addition, a sufficient amount of the alkali metal and ammo from about 0.005 to about 3 parts by weight (based on the nium salts and hydroxides are generally included to increase weight of the salt or hydroxide and not the salt or hydroxide the pH of the overall composition to a pH of at least about Solution). Because the alkali metal and ammonium salts and 10 9. If an alkali metal or ammonium salt is used that cannot hydroxides added to the composition are added in aqueous produce the desired pH in Solution Such as the salt of a strong solution, the salts and hydroxide of the invention are water acid and strong base (e.g. sodium Sulfate), at least one alkali soluble and preferably have a in water at 20°C. of metal or ammonium salt or hydroxide that provides alka greater than about 10 g/100 mL. The salts for use in the linity to the composition, i.e., a base Such as sodium hydrox invention include but are not limited to Sulfates, carbonates, 15 ide or the salt of a weak acid and strong base such as sodium silicates, phosphates, phosphites, borates, fluorides, Sulfites, carbonate, is preferably additionally included to provide the oxalates and citrates. Suitable alkali metal and ammonium desired pH. salts and hydroxides for use in the invention include but are At least one compound preferably selected from the group not limited to sodium hydroxide (NaOH), sodium sulfate consisting of Group IIA (e.g. Be, Mg, Ca, Sr., Ba), Group (NaSO), (NaHSO), sodium carbonate IIIA (e.g. Sc, La), Group IIIB (e.g. Al. Ga, In), copper, Zinc, (NaCO), sodium bicarbonate (NaHCO), sodium metasili cadmium, manganese, iron, cobalt and nickel salts is also cate (Na2SiO), Sodium disilicate (Na2SiO5), sodium ortho added to the composition. In addition, water-soluble salts silicate (NaSiO), sodium orthophosphate (NaPO), diso having other cations can be used in accordance with the dium hydrogen phosphate (NaHPO), sodium dihydrogen invention that react with the alkali metal and (NaH2PO4), hexasodium metaphosphate 25 salts and hydroxides to produce a salt or hydroxide having ((NaPO)), trisodium metaphosphate ((NaPO)), sodium a solubility in water at 20° C. of less than about 0.5 g/100 triphosphate (Nasp.O), Sodium hypophosphite mL. The Group IIA, Group IIIA, Group IIIB, copper, zinc, (NaH2PO), Sodium dihydrogen orthophosphite cadmium, manganese, iron, cobalt and nickel salts are (NaH2PO), sodium metaborate (NaBO), sodium sulfite preferably added to the composition in aqueous Solution in (NaSO), sodium citrate (NaCHO7), potassium hydrox 30 an amount from greater than 0 to about 2 parts by weight, ide (KOH), potassium sulfate (KSO), more preferably, in an amount from about 0.001 to about 1 (KHSO), potassium carbonate (KCO), potassium bicar part by weight (based on the weight of the salt). Preferably, bonate (KHCO), potassium sodium carbonate (KNaCO), the Group IIA, Group IIIA, Group IIIB, copper, zinc, potassium metasilicate (KSiO), potassium tetrasilicate cadmium, manganese, iron, cobalt and nickel salts added to (KSiO), potassium orthophosphate (KPO), dipotassium 35 the composition of the invention are water-soluble and hydrogen phosphate (KHPO), potassium dihydrogen preferably have a solubility in water at 20°C. of greater than phosphate (KH2PO4), hexapotassium metaphosphate about 10 g/100 mL. For example, the Group IIA, Group ((KPO)), tetrapotassium metaphosphate ((KPO)4), potas IIIA, Group IIIB, copper, Zinc, cadmium, manganese, iron, sium pyrophosphate (KPO), potassium Subphosphate cobalt and nickel salts can be chlorides, Sulfates or nitrates. (KPO), potassium hypophosphite (KHPO), potassium 40 Suitable Group IIA, Group IIIA, Group IIIB, copper, zinc, dihydrogen orthophosphite (KHPO), potassium metabo cadmium, manganese, iron, cobalt and nickel salts include rate (KBO), potassium tetraborate (KBO7), potassium but are not limited to calcium chloride (CaCl), calcium fluoride (KF), potassium sulfite (KSO), potassium hydro nitrate (Ca(NO)), magnesium chloride (MgCl), magne gen Sulfite (KHSO), potassium citrate (KCHO), sium nitrate (Mg(NO)), magnesium Sulfate (MgSO4), alu monobasic potassium citrate (KHCHO), ammonium 45 minum chloride (AICl), aluminum nitrate (Al(NO)), alu hydroxide (NH-OH), ((NH4)2SO), minum sulfate (Al2(SO4)), beryllium chloride (BeCl), (NHHSO), beryllium nitrate (Be(NO)), beryllium sulfate (BeSO), ((NH4)2CO), (NHHCO), ammo copper (II) chloride (CuCl2), copper(II) nitrate (Cu(NO)), nium orthophosphate ((NH4)PO), diammonium hydrogen copper (II) sulfate (CuSO), strontium chloride (SrCl), phosphate ((NH4)HPO), ammonium dihydrogen phos 50 strontium nitrate (Sr(NO)), barium chloride (BaCl), phate (NHHPO), ammonium Sodium phosphate barium nitrate (Ba(NO)), Zinc chloride (ZnCl2), Zinc (NaNHHPO), ammonium hypophosphite (NHHPO), nitrate (Zn(NO)), Zinc sulfate (ZnSO), cadmium chloride ammonium dihydrogen orthophosphite (NHHPO), (CdCl2), cadmium nitrate (Cd(NO)), cadmium sulfate (NHF), ((NH), (CdSO), scandium chloride (ScCl), scandium nitrate (Sc SO), ammonium bisulfite (NHHSO), ammonium binox 55 (NO)), Scandium sulfate (Sc.(SO4)), gallium chloride alate (NHHCO), diammonium citrate ((NH4)HCHO) (GaCl), gallium nitrate (Ga(NO)), gallium sulfate (Ga. and ((NH4). CHO,). Preferably, the (SO4)), indium chloride (InCl), indium nitrate (InCNO)), alkali metal and ammonium salts and hydroxides are salts indium sulfate (In(SO4)), lanthanum chloride (LaCl), and hydroxides of sodium, potassium and ammonium and, lanthanum nitrate (La(NO)), manganese (II) chloride more preferably, are hydroxides, Sulfates, carbonates, sili 60 (MnCl2), manganese (II) nitrate (Mn(NO)), manganese cates and phosphates of sodium, potassium and ammonium. (II) sulfate (MnSO), iron (II) chloride (FeCl), iron (II) In a preferred embodiment, the alkali metal and (Fe(NO)), iron (II) sulfate (FeSO), iron (III) salts and hydroxides include sodium hydroxide. The alkali chloride (FeCl), iron (III) nitrate (Fe(NO)), iron (III) metal and ammonium salts and hydroxides can be provided sulfate (Fe(SO4)), cobalt(II) chloride (COCl), cobalt(II) in hydrated or anhydrous form for use in the invention. 65 nitrate (Co(NO)), cobalt(II) sulfate (CoSO), cobalt(III) The alkali metal and ammonium salts and hydroxides chloride (COCl), nickel chloride (NiCl), nickel nitrate provide cations that react with the Group IIA, Group IIIA, (Ni(NO)), and nickel sulfate (NiSO4). Preferably, the US 7,250,460 B1 5 6 Group IIA, Group IIIA, Group IIIB, copper, zinc, cadmium, (Ba(CHO)), Zinc hydroxide (Zn(OH)), Zinc carbonate manganese, iron, cobalt and nickel salts are calcium, mag (ZnCO), zinc silicate (2ZnO SiO), zinc metasilicate (Zn nesium or aluminum salts such as calcium chloride (CaCl), SiO), Zinc orthosilicate (Zn2SiO4), Zinc orthophosphate calcium nitrate (Ca(NO)), magnesium chloride (MgCl). (Zn(PO4)), Zinc pyrophosphate (Zn-PO7), Zinc sulfite magnesium nitrate (Mg(NO)), magnesium Sulfate (ZnSOs), Zinc oxalate (ZnCO), Zinc citrate (Zn(CHS (MgSO4), aluminum chloride (AICl), aluminum nitrate O)), cadmium hydroxide (Cd(OH)), cadmium carbonate (Al(NO)), and aluminum sulfate (Al(SO4)). More pref (CdCO), cadmium metasilicate (CdSiO), cadmium ortho erably, the Group IIA, Group IIIA, Group IIIB, copper, zinc, phosphate (Cd (PO4)), cadmium pyrophosphate cadmium, manganese, iron, cobalt and nickel salts include (Cd PO7), cadmium dihydrogen phosphate (CdCHPO)). calcium chloride or calcium nitrate. The Group IIA, Group 10 cadmium sulfite (CdSOs), cadmium oxalate (CdCO), IIIA, Group IIIB, copper, Zinc, cadmium, manganese, iron, scandium hydroxide (Sc(OH)), gallium hydroxide (Ga cobalt and nickel salts can be provided in hydrated or (OH)), gallium fluoride (GaF), gallium oxalate (Ga. anhydrous form. (CO)), indium hydroxide (In?(OH)), indium fluoride The alkali metal and ammonium salts and hydroxides (InF), lanthanum hydroxide (La(OH)), lanthanum carbon added to the composition react with the Group IIA, Group 15 ate (La(CO3)), lanthanum oxalate (La (C2O4)), manga IIIA, Group IIIB, copper, Zinc, cadmium, manganese, iron, nese (II) hydroxide (Mn(OH)), manganese (III) hydroxide cobalt and nickel salts added to the composition to produce (Mn(OH)), manganese (II) carbonate (MnCO), manganese at least one Group IIA, Group IIIA, Group IIIB, copper, (II) metasilicate (MnSiO), manganese (II) monohydrogen Zinc, cadmium, manganese, iron, cobalt or nickel salt or orthophosphate (MnHPO), manganese (III) orthophosphate hydroxide having a low solubility in water (if any). Prefer (MnPO), manganese (III) metaphosphate (Mn(POs)), ably, the Group IIA, Group IIIA, Group IIIB, copper, zinc, manganese (II) pyrophosphate (MnPO7), manganese (II) cadmium, manganese, iron, cobalt and nickel salts or orthophosphite (MnHPO), manganese (II) oxalate hydroxides produced by the reaction have a solubility in (MnCO), manganese (II) citrate (Mn(CHsO4)), iron (II) water at 20° C. of less than about 0.5 g/100 mL. For hydroxide (Fe(OH)), iron (II) carbonate (FeCO), iron (II) example, the Group IIA, Group IIIA, Group IIIB, copper, 25 metasilicate (FeSiO), iron (II) orthosilicate (Fe2SiO4), iron Zinc, cadmium, manganese, iron, cobalt and nickel salts and (II) orthophosphate (Fe hydroxides produced by the reaction of the salts added to the (PO)), iron (III) orthophosphate (FePO), iron (III) ortho composition include but are not limited to calcium hydrox phosphate (FePO), iron (III) pyrophosphate (Fe(PO)), ide (Ca(OH)), calcium sulfate (CaSO), calcium carbonate iron (III) hypophosphite (Fe(HPO)), iron (II) fluoride (CaCO), calcium metasilicate (CaSiO), calcium orthosili 30 (FeF), iron (III) fluoride (FeF), iron (II) sulfite (FeSO), cate (Ca2SiO4), tricalcium silicate (3CaO SiO2), calcium iron(II) oxalate (FeCO), iron (II) citrate (FeC.H.O.), iron orthophosphate (Cas (PO)), dicalcium orthophosphate (III) citrate (FeCHO), cobalt (II) hydroxide (Co(OH)), (CaFIPO), monocalcium orthophosphate (Ca(HPO)), cobalt (III) hydroxide (Co(OH)), cobalt (II) carbonate calcium hypophosphate (CaPO), calcium metaphosphate (CoCO), cobalt (III) carbonate (Co(CO)), cobalt (II) (Ca(PO)), calcium pyrophosphate (CalPO7), calcium 35 orthosilicate (CoSiO), cobalt (II) orthophosphate (Co. orthophosphite (CaHPO), calcium tetraborate (CaBO7), (PO)), cobalt (II) sulfite (CoSO), cobalt (II) oxalate calcium metaborate (Ca(BO)), calcium fluoride (CaF2). (CoCO), nickel hydroxide (Ni(OH)), nickel carbonate calcium Sulfite (CaSO), calcium oxalate (CaCO), calcium (NiCO), nickel orthophosphate (Ni(PO)), nickel sulfite citrate (Ca(CHO)), aluminum hydroxide (Al(OH)), (NiSO) and nickel oxalate (NiCO). Typically, because the aluminum silicate (Al-O-SiO or 3Al-O 2SiO2), aluminum 40 calcium, magnesium and aluminum salts are preferred, the orthophosphate (AlPO), aluminum fluoride (AlF), alumi composition includes one or more of the above calcium, num oxalate (Al2(CO)), magnesium hydroxide magnesium or aluminum salts. The alkali metal and ammo (Mg(OH)), magnesium carbonate (MgCO), magnesium nium salts resulting from the reaction typically include one metasilicate (MgSiO), magnesium orthosilicate or more of sodium chloride, Sodium sulfate, Sodium nitrate, (MgSiO4), magnesium orthophosphate (Mg(PO4)), mag 45 potassium chloride, potassium Sulfate, potassium nitrate, nesium monohydrogen orthophosphate (MgHPO), magne , ammonium sulfate or ammonium sium pyrophosphate (Mg-PO7), magnesium orthophosphite nitrate. (MgHPO), magnesium metaborate (Mg(BO)), magne Some exemplary combinations of the alkali metal and sium orthoborate (Mg(BO)), magnesium fluoride ammonium salts or hydroxides and the Group IIA, Group (MgF2), magnesium oxalate (MgCO), beryllium hydrox 50 IIIA, Group IIIB, copper, Zinc, cadmium, manganese, iron, ide (Be(OH)), beryllium carbonate (BeCO), beryllium cobalt and nickel salts added to the composition include the orthosilicate (BeSiO4), copper (II) hydroxide (Cu(OH)), following: I+V, II+V, III+V, IV+V. I+IV+V. I+VI, II+VI, copper (II) carbonate (CuCO), copper (II) orthophosphate III+VI, I+VII, II+VII, and III+VII, wherein: (Cu(PO)), copper (I) fluoride (CuF), copper (II) oxalate I. Sodium hydroxide, sodium carbonate, sodium silicate (CuCO), copper citrate (CuCHO), strontium hydrox 55 and/or sodium phosphate; ide (Sr(OH)), strontium sulfate (SrSO), strontium carbon II. potassium hydroxide, potassium carbonate, potassium ate (SrCO), strontium metosilicate (SrSiO), strontium silicate and/or potassium phosphate: orthosilicate (SrSiO4), strontium orthophosphate (Sr. III. ammonium hydroxide, ammonium carbonate, ammo (PO4)), strontium monohydrogen orthophosphate nium silicate and/or ammonium phosphate; (SrHPO), strontium tetraborate (SrBO), strontium fluo 60 ride (SrE), strontium sulfite (SrSO), strontium oxalate IV. Sodium sulfate, potassium sulfate and/or ammonium (SrCO), barium sulfate (BaSO), barium carbonate sulfate; (BaCO), barium metasilicate (BaSiO), barium monohy V. calcium chloride and/or calcium nitrate; drogen orthophosphate (BaFIPO), tribarium orthophos VI. magnesium chloride, magnesium nitrate and/or magne phate (Ba(PO)), barium hypophosphate (BaPO), barium 65 sium Sulfate; and pyrophosphate (Ba-PO7), barium fluoride (BaF), barium VII. aluminum chloride, aluminum nitrate and/or aluminum sulfite (BaSO), barium oxalate (BaCO), barium citrate sulfate. US 7,250,460 B1 7 8 More preferably, the first compound includes ammonium The present invention will now be further described by or sodium salts or hydroxide (e.g. ammonium hydroxide or the following non-limiting examples. Except where other NaOH) and the second compound includes calcium chloride wise indicated, percentages are on a per weight basis and and/or calcium nitrate. Solutions are aqueous Solutions. Furthermore, the alkali metal and ammonium salts and 5 It is understood that upon reading the above description of hydroxides listed above and other alkali metal and ammo the present invention, one skilled in the art could make nium salts can be combined with the Group IIA, Group IIIA, changes and variations therefrom. These changes and varia Group IIIB, copper, Zinc, cadmium, manganese, iron, cobalt tions are included in the spirit and scope of the following and nickel salts listed above or any other Group IIA, Group appended claims. IIIA, Group IIIB, copper, Zinc, cadmium, manganese, iron, 10 cobalt and nickel salts in many other combinations in EXAMPLE 1. accordance with the invention to provide the desired pH and a Group IIA, Group IIIA, Group IIIB, copper, zinc, cad 5 g of 30% aqueous CaCl (calcium chloride) solution mium, manganese, iron, cobalt and nickel salt or hydroxide was added into an equal amount of 35% aqueous (NH) 15 HPO, (ammonium biphosphate) solution. Fine white precipi having a low solubility in water. tate formed immediately upon addition of drops of ammo The order of addition is not critical, but preferred such nium biphosphate solution into the calcium chloride solu that the addition of the first compound would not signifi tion. Precipitates were diluted with water and optical cantly change the latex pH or coagulate it. The at least one microscope observation showed the presence of fine plate first compound can be added before, after, or at the same lets of less than 1 micrometer thick and 3-5 micrometer time as the at least one second compound. If a cationic latex length as shown in FIG. 1. is used, the pH is generally 4-5, so the hydroxide or salts should be added as the second compound to prevent pH EXAMPLE 2 increase, which may cause increase in the latex viscosity. To prevent coagulation, incremental amounts of the at least one 5 g of 30% aqueous CaCl (calcium chloride) solution first compound and the at least one second compound can be 25 was added into 100 g of cationic styrene-butadiene latex, made until the entire amount of each is added. Also, the at BUTONAL(R) NX1118 from BASF Corporation. The latex least one first compound and the at least one second com remained as a stable dispersion. After mixing, 5g of 35% pound could be mixed together and added to the latex. aqueous (NH4)HPO (ammonium biphosphate) solution The alkali metal or ammonium salts or hydroxides in the was added under agitation. The latex pH remained below 4.5 composition include the salts formed by the reaction 30 during and at the end of (NH4)HPO addition. This proce between the salts and hydroxides added to the composition dure was expected to produce approximately 2 wt % of as discussed above. Excess alkali metal and ammonium salts calcium phosphate (Ca-phosphate) nano-crystals in the latex and hydroxides added to the composition Such as sodium polymer. A thin latex film of approximately 250 um was hydroxide are typically also present, particularly if desired to prepared by diluting the latex dispersion from 65% solids to maintain the pH of the composition at a pH of at least about 35 45% solids with water, spreading the dispersion on a poly 9. The composition also includes at least one Group IIA, tetrafluoroethylene plate, and drying at room temperature. Group IIIA, Group IIIB, copper, Zinc, cadmium, manganese, Masking tape was applied at four corners of the plate to keep iron, cobalt or nickel salt or hydroxide having low water the latex dispersion wetting the plate. After completely solubility, e.g., a solubility in water at 20° C. of less than drying, the film was cut to expose a thin cross-section, and about 0.5 g/100 mL, and exemplary salts and hydroxides are 40 the cross-section was observed under the optical micro mentioned above. The Group IIA, Group IIIA, Group IIIB, Scope. The presence of fine nano-crystals was apparent in copper, Zinc, cadmium, manganese, iron, cobalt and nickel the entire polymer film as shown in FIG. 2. salts added to the composition (e.g. calcium chloride) can EXAMPLE 3 also be present in Small amounts. 45 The latex can be dried to provide a nanocomposite film. The latex dispersion prepared in Example 2 was dried for The drying can be accomplished by any drying method. The one day at room temperature to prepare the latex film as film has increased tensile strength, elongation, and heat described above, then cured in an oven at 60° C. for 24 resistance as compared to a film prepared without the hours. As comparison, a latex film was also prepared from nanoparticles. The film prepared with this nanoparticles are 50 BUTONAL(R) NX1118 latex without addition of calcium especially unique of achieving significantly improved elon chloride or ammonium biphosphate solutions. These latex gation without reducing the tensile strength. Generally, a films were cut to rectangular latex films of approximately 3 polymer film of lower tensile strength has a high elongation, mm wide and 25 mm long. The tensile strength of the films but a stronger polymer has a limited elongation. This nano with and without Ca-phosphate crystals was determined. particle modified film prepared by the method of the inven 55 Measured tensile strength of these latex films were shown tion maintains the same or slightly higher tensile strength in FIG. 3a. The BUTONAL(R) NX1118 latex was not fully with significantly improved elongation as compared to a dried with the above described condition and the film had latex that was not modified by the method of the invention. only limited strength of slightly below 0.5 MPa peak As shown above, there are a number of possible combi strength and broken at about 250% elongation. The film nations of alkali metal and ammonium salts and hydroxides 60 developed a thin filament (necking) under elongation and and Group IIA, Group IIIA, Group IIIB, copper, zinc, broke from that weak point. In contrast, the 2% Ca-phos cadmium, manganese, iron, cobalt and nickel salts that can phate nano-crystal modified latex film did not develop the be used in accordance with the invention. Therefore, there is necking and maintained its original dimension during elon a lot of flexibility in the method of the present invention in gation even at above 3,000% elongation and the tensile selecting salts for the preparation of the compositions. In 65 strength reached nearly 0.6 MPa at this elongation. The latex addition, the amounts of each salt used can affect the film did not break at 3,200% elongation, which was the limit resulting compositions. of the instrument used. US 7,250,460 B1 10 The above-described latex films were soaked in water for aged for 40 minutes in a forced airflow oven at 160° C. A one day, and the tensile strength measured. Excess water was latex film of BUTONAL(RDNS198 latex was also prepared absorbed with paper towel prior of the measurement. The and heat aged at the same condition. The BUTONAL(R) tensile strength of the BUTONAL(R) NX1118 latex film NS198 latex film became dark brown after 40 minutes of dropped to below 0.4 MPa peak strength after immersing in 5 heat aging, but the Ca-phosphate nano-crystal modified film water for 24 hours, and it broke at about 200% elongation was lighter color than the unmodified film. The tensile (FIG. 3b). The Ca-phosphate modified latex film also lost strength of both latex films was determined and results are peak strength, but maintained 0.2 MPa strength above shown in FIG. 7. The unmodified film broke at slightly 1,000% elongation and did not break even at 3,200% above 2100% elongation, but the Ca-phosphate nano-crystal elongation. 10 modified film did not break even at 3000% elongation. What is claimed is: EXAMPLE 4 1. A method of forming a composition comprising adding at least one first compound in an amount from greater than 5 g of 30% aqueous CaCl (calcium chloride) solution 0 to about 4 parts by weight of the composition that is at least was added into 100 g of cationic styrene-butadiene latex, 15 one of an alkali metal salt, an ammonium salt, an alkali BUTONAL(R) NS198 from BASF Corporation. The latex metal hydroxide, or an ammonium hydroxide and at least dispersion was dried for 6 days at room temperature and one second compound in an amount from greater than 0 to cured in an oven at 60° C. for 24 hours. As comparison, the about 2 parts by weight of the composition that is at least one latex film was also prepared with BUTONAL(R) NS198 latex of a Group IIA salt, a Group IIIA salt, a Group IIIB salt, a without calcium chloride or ammonium biphosphate solu copper salt, a Zinc salt, a cadmium salt, a manganese salt, an tions. The tensile strength of these films was determined as iron salt, a cobalt salt, or a nickel salt to a latex, wherein the in Example 3 and results are shown in FIG. 4. The latex film salts of the at least one second compound are selected from of the BUTONAL(R) NS198 latex showed slightly above 0.4 the group consisting of chlorides, sulfates, nitrates, and MPa maximum tensile strength and the film broke at slightly combinations thereof, and the latex remains a stable disper above 500% elongation. In contrast, the latex film with 25 S1O. Ca-phosphate nano-crystals did not break even at 3000% 2. The method of claim 1 further comprising drying the elongation at the maximum tensile strength of 0.45 MPa. composition. 3. The method of claim 1, wherein the at least one first EXAMPLE 5 compound is added before the at least one second com 30 pound. The latex film of BUTONAL(R) NX1118 modified with 4. The method of claim 1, wherein the at least one second Ca-phosphate nano-crystals was prepared as in Example 3, compound is added before the at least one first compound. but it was dried for 6 days at room temperature and then 5. The method of claim 1, wherein the salts of the at least placed in an oven at 100° C. for 3 hours. The latex film one first compound are selected from the group consisting of showed only slight discoloration to light brown after 3 hours 35 Sulfates, carbonates, silicates, phosphates, phosphites, of heat aging. In comparison, the latex film of the borates, fluorides, Sulfites, oxalates, citrates, and combina BUTONAL(R) NX1118 latex became brown after the same tions thereof. heat treatment. The latex film modified with Ca-phosphate 6. The method of claim 1, wherein the alkali metal of the nano-crystals maintained above 3000% elongation after the at least one first compound is at least one of sodium or heat treatment. In contrast, the unmodified BUTONAL(R) 40 potassium. NX1118 latex film was broken at slightly above 2100% 7. The method of claim 1, wherein the at least one first elongation. compound is selected from the group consisting of Sodium hydroxide (NaOH), sodium sulfate (Na2SO), sodium bisul EXAMPLE 6 fate (NaHSO), sodium carbonate (NaCO), sodium bicar 45 bonate (NaHCO), sodium metasilicate (NaSiO), sodium Ca-phosphate nano-crystal modified and unmodified disilicate (Na2Si2Os), sodium orthosilicate (NaaSiO4), BUTONAL(R) NX1118 latex films were prepared as in sodium orthophosphate (NaPO), disodium hydrogen phos Example 5, but after drying 6 days at room temperature, the phate (NaHPO), sodium dihydrogen phosphate films were placed in a forced airflow oven at 160° C. for 20 (NaH2PO), hexasodium metaphosphate ((NaPO)), triso minutes. The unmodified BUTONAL(R) NX1118 latex film 50 dium metaphosphate ((NaPO)), Sodium triphosphate discolored and had a brown color. The Ca-phosphate nano (NaspOo), Sodium hypophosphite (NaH2PO), Sodium crystal modified film showed only slight discoloration. The dihydrogen orthophosphite (NaH2PO), sodium metaborate latex films were also heat aged for 40 minutes at the same (NaBO), sodium sulfite (NaSO), sodium citrate condition. The unmodified latex film became dark brown (NaCHsO4), potassium hydroxide (KOH), potassium sul after 40 minutes of heat aging, but the Ca-phosphate nano 55 fate (K2SO4), potassium bisulfate (KHSO4), potassium car crystal modified one showed less discoloration. bonate (KCO), potassium bicarbonate (KHCO), potas The tensile strength of the latex film and the Ca-phosphate sium sodium carbonate (KNaCO), potassium metasilicate nano-crystal modified film were determined after 20 minutes (K2SiO), potassium tetrasilicate (KSiO), potassium and 40 minutes heat aging at 160° C. (FIGS. 6a and b). The orthophosphate (KPO), dipotassium hydrogen phosphate Ca-phosphate modified films maintained above 3000% elon 60 (KHPO), potassium dihydrogen phosphate (KHPO), gation even after these severe heat agings. hexapotassium metaphosphate ((KPO)), tetrapotassium metaphosphate ((KPO)4), potassium pyrophosphate EXAMPLE 7 (KPO7), potassium subphosphate (KPO), potassium hypophosphite (KHPO), potassium dihydrogen ortho BUTONAL(R) NS198 latex modified with Ca-phosphate 65 phosphite (KHPO), potassium metaborate (KBO), potas nano-crystals was prepared as in Example 4. This latex sium tetraborate (KBO), potassium fluoride (KF), potas dispersion was dried for 6 days at room temperature and heat sium sulfite (KSO), potassium hydrogen sulfite (KHSO), US 7,250,460 B1 11 12 potassium citrate (KCHO), monobasic potassium citrate (II) nitrate (Mn(NO)), manganese (II) sulfate (MnSO), (KHCHO), ammonium hydroxide (NH-OH), ammo iron (II) chloride (FeCl), iron (II) nitrate (Fe(NO)), iron nium sulfate ((NH4)2SO4), ammonium bisulfate (II) sulfate (FeSO4), iron (III) chloride (FeCl), iron (III) (NHHSO), ammonium carbonate ((NH4)2CO), ammo nitrate (Fe(NO)), iron (III) sulfate (Fe(SO4)), cobalt(II) nium bicarbonate (NHHCO), ammonium orthophosphate chloride (CoCl), cobalt (II) nitrate (Co(NO)), cobalt(II) ((NH4)PO), diammonium hydrogen phosphate ((NH4) sulfate (CoSO), cobalt (III) chloride (COCl), nickel chlo HPO), ammonium dihydrogen phosphate (NHHPO), ride (NiCl), nickel nitrate (Ni(NO)), nickel sulfate ammonium sodium phosphate (NaNHHPO), ammonium (NiSO), and combinations thereof. hypophosphite (NHHPO), ammonium dihydrogen ortho 9. The method of claim 1, wherein combinations of the at phosphite (NHHPO), ammonium fluoride (NHF), 10 least one first compound and the at least one second com ammonium Sulfite ((NH4)2SO), ammonium bisulfite pound are selected from the group consisting of I+V, II+V. (NHHSO), ammonium binoxalate (NHHCO), diammo III+V, IV+V, I+IV+V, I+VI, II+VI, III+VI, I+VII, II+VII, nium citrate ((NH4)HCHO), triammonium citrate and III+VII, wherein ((NH)-CHsO4), and combinations thereof. I) at least one of sodium hydroxide, sodium carbonate, 8. The method of claim 1, wherein the at least one second 15 Sodium silicate, and/or sodium phosphate: compound is selected from the group consisting of calcium II) at least one of potassium hydroxide, potassium car chloride (CaCl), calcium nitrate (Ca(NO)), magnesium bonate, potassium silicate, and/or potassium phosphate; chloride (MgCl), magnesium nitrate (Mg(NO)), magne III) at least one of ammonium hydroxide, ammonium sium Sulfate (MgSO4), aluminum chloride (AICl), alumi carbonate, ammonium silicate, and/or ammonium num nitrate (Al(NO)), aluminum Sulfate (Al2(SO4)), phosphate; beryllium chloride (BeCl), beryllium nitrate (Be(NO)), beryllium sulfate (BeSO), copper (II) chloride (CuCl2). IV) at least one of Sodium sulfate, potassium sulfate, copper(II) nitrate (Cu(NO)), copper(II) sulfate (CuSO), and/or ammonium Sulfate; strontium chloride (SrCl), strontium nitrate (Sr(NO)), V) at least one of calcium chloride and/or calcium nitrate; barium chloride (BaCl), barium nitrate (Ba(NO)), Zinc 25 VI) at least one of magnesium chloride, magnesium chloride (ZnCl2), Zinc nitrate (Zn(NO)), Zinc sulfate nitrate, and/or magnesium sulfate; and (ZnSO), cadmium chloride (CdCl2), cadmium nitrate (Cd VII) at least one of aluminum chloride, aluminum nitrate, (NO)), cadmium sulfate (CdSO), scandium chloride and/or aluminum Sulfate. (ScCl), Scandium nitrate (Sc(NO)), Scandium Sulfate (Sc. 10. The method of claim 1, wherein the at least one first (SO)), gallium chloride (GaCl), gallium nitrate 30 compound is at least one of a sodium salt or Sodium (Ga(NO)), gallium sulfate (Ga(SO4)), indium chloride hydroxide, and the at least one second compound is at least (InCl), indium nitrate (In(NO)), indium sulfate (In one of calcium chloride and/or calcium nitrate. (SO)), lanthanum chloride (LaCl), lanthanum nitrate (La(NO)), manganese (II) chloride (MnCl2), manganese