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United States Patent (113,627,798 72 Inventor Laird Gordon Lindsay Ward 3,321,502 5/1967 Soeder ...... 260/439 Suffern, N.Y. (21) Appl. No. 869,905 3,346,447 10/1967 Wright...... - - 167/31 22 Filed Oct. 27, 1969 3,390,160 6/1968 Heller et al.. 260/433 45) Patented Dec. 14, 1971 3,437,620 4/1969 Yamamoto...... 260/23 (73) Assignee The International Nickel Company, Inc. OTHER REFERENCES New York, N.Y. Teramura et al. Chem. Abst. 68 p. 1360, abstract of Japanese Patent 5424- (67) Kirk- Othmer, Encyclopedia of Chemical Technology In (54) PROCESS FOR PREPARING THE NICKEL terscience Publishers, N.Y., N.Y., Vol. 13, 1967, p. 754-755 DERVATIVES OF METHYLENEBSPHENOL Primary Examiner-Tobias E. Levow 11 Claims, NoDrawings Assistant Examiner-A. P. Demers 52) U.S. Cl...... 260/439 R, Attorney-Maurice L. Pinel 260/45.75 N (51) int. Cl...... C07f 15/04, C08f 45/62 ABSTRACT: A process for preparing nickel derivatives of (50) Field of Search...... 260/439, methylene bisphenols in which a methylene bisphenol, a 45.75 N; 252/42.7 Group a metal alkoxide and a nickel salt are reacted in an es sentially nonaqueous environment, and the nickel derivative is (56) References Cited precipitated from solution. Novel nickel derivatives of UNITED STATES PATENTS methylene bisphenol, e.g., nickel hexachlorophene, are effec 2,971,968 2/1961 Nicholson et al...... 260/439 tive as light stabilizing additives in vinyl polymers. 3,627,798 1 2 PROCESS FOR PREPARNGTHENICKELDERVATIVES ing of , ethanol, propanol, isopropanol, n-butanol, OFMETHYLENEBSPHENOL isobutanol, sec-butanol, acetone, tetrahydrofuran, dimethox This invention relates to a novel process for preparing yethane and dimethylformamide; and precipitating the nickel nickel compounds which are derivatives of methylene derivative. bisphenols and, more particularly, to novel stabilizing com 5 The methylene bisphenol used in the process is beneficially pounds for vinyl polymers, such as polyvinylchloride. hexachlorophene having the general structure, Attempts to prepare nickel salts of methylene bisphenols, HO OH such as hexachlorophene, in aqueous media, have thus far not met with success. It is desirable that a method suitable for the Cl -CH- -Cl preparation of such compounds be provided. O Polyvinylchloride (PVC) and related vinyl polymers are -Cl Cl light sensitive and suffer degradation including both discolora tion and embrittlement upon exposure to light, Many attempts Cl Cl have been made to stabilize these polymers by introducing although other suitable methylene bisphenols can be em various additives, and improvement in the stability of these 15 ployed. With regard to the Group a metal alkoxide, materials upon exposure to light has been achieved in some and cesium are highly reactive Group a metals and for that cases. However, more effective and more economical stabil reason are less desirable for the contemplated reaction to izers are needed. produce an alkoxide. Also, rubidium is not very solu A new process has now been discovered in which a ble in alcohol, and cesium chloride is quite hygroscopic, these methylene bisphenol, a Group a metal alkoxide and a nickel 20 properties being disadvantageous in the reactions of the inven are reacted to precipitate a nickel derivative of tion as will be more fully explained hereinafter. While the an methylene bisphenol. hydrous nickel halide can be used in its pure form as a reac It has further been discovered that the novel compounds tant to the extent that it is soluble in the nonaqueous solvent, it prepared by the process of the invention are useful as light sta is advantageous to provide the nickel halide in the more solu bilizers for vinyl polymers. 25 ble form of an anhydrous organic complex. Such a soluble or It is an object of the invention to provide a process for mak ganic complex may be prepared by reacting the hydrated ing the nickel derivative of hexachlorophene. nickel halide (chloride, bromide or iodide) with peroxide Another object of the invention is to provide a vinyl free, ethylene-glycol dimethylether (monoglyme). The polymer having improved stabilization characteristics against 30 product of this reaction is nickel halide dimethoxyethanate degradation by light. (nickel halide. EGDE complex). The nickel halide. EGDE Other objects and advantages will become apparent from complex is quite soluble in alcohol and it is also soluble in the following description. acetone, tetrahydrofuran, dimethoxyethane and dimethyl Generally speaking, the present invention contemplates a formamide. process for making nickel derivatives of methylene bisphenols 35 The alcohols employed in the process, which desirably con having the general formula, tain from one to four carbon atoms, may function as solvents as well as reactants, i.e., the stoichiometric amount of alcohol HO O-Ni-O gh functioning as a reactant while the excess alcohol functions as a solvent. Alcohols having more than four carbons atoms are R CH R. R- CH R 40 less reactive at the reaction temperatures characterizing this process and, for that reason, are not as well suited for use as R -R. R. -R. R. -R. R. -R solvents, although they will react with the . Al cohols having up to 12 carbon atoms may be used as reactants, R R R R but the increasing viscosity of the higher alcohols, e.g., 45 isoamyl alcohol, slows the desired reactions, and the system may have to be heated to obtain the reaction. Further, no par in which R is selected from the group consisting of hydrogen; ticular benefit is secured by employing the higher alcohols. , e.g., ; alkyls, e.g., butyl; substituted alkyls, Under normal conditions, the tert-butyl alcohol does not react e.g., tertiary butyl; aryls, e.g., phenyl; alkylaryls, e.g., with lithium or sodium. methylphenyl; arylalkyls, e.g., benzyl; or combinations 50 In order to obtain a relatively pure product upon precipita thereof. The compounds provided in accordance with the in tion of the nickel derivatives of methylene bisphenols from vention are useful as light stabilizing additives for vinyl solution, it will be understood that the byproduct of the reac polymers such as polyvinylchloride and polyvinyl acetate. tion, i.e., the , must be soluble in the solvent More particularly, the nickel derivatives of methylene employed to facilitate separation of the product from the bisphenols are prepared by reacting a methylene bisphenol 55 byproduct. Since alcohols are advantageous solvents, it will be having the general formula, apparent that reactants which result in the production of HO OH byproducts which are relatively insoluble, or only slightly solu ble, in alcohol, such as lithium fluoride, sodium fluoride, sodi R- -CH- -R um chloride, sodium bromide, potassium fluoride, potassium 60 chloride, potassium bromide , rubidium bro R -R. R. -R mide and cesium fluoride, are unsuitable for the practice of this process, if an alcohol is used assolvent. R R It is possible, though less convenient, to use other solvents in which R is selected from the group consisting of hydrogen; 65 in the process (with alcohol functioning only as a reactant) in halogens, e.g., chlorine; alkyls, e.g., butyl; substituted alkyls, cluding acetone, tetrahydrofuran, dimethoxyethane and e.g., tertiary butyl; aryls, e.g., phenyl; alkylaryls, e.g., dimethylformamide. The nickel halide EGDE complex and methylphenyl; arylalkyls, e.g., benzyl; or combinations the byproduct alkali metal such as , thereof; a Group a metal alkoxide, which advantageously is lithium iodide, lithium bromide, sodium iodide, potassium the reaction product of a Group a metal, e.g., lithium, sodium 70 iodide, , cesium chloride, cesium bromide and or potassium, and an alcohol having from one to four carbon cesium iodide will dissolve in these solvents. atoms, e.g., methanol, ethanol, propanol, isopropanol, n-bu The sequence in which the reactions of the invention are tanol, isobutanol or sec-butanol; and an anhydrous, or sub conducted is of significant importance. Thus, the methylene stantially anhydrous, nickel halide; in an essentially nonaque bisphenol is first reacted with the Group a metal alkoxide to ous solvent, particularly one selected from the group consist 75 form a Group a metal methylene bisphenolate. The Group a 3,627,798 3 4. metal methylene bisphenolate is reacted with a nickel dihalide Preparation of Nickel Hexachlorophenate whereupon the Group a metal of two molecules of the bisphenolate are replaced by nickel which links the two Nickel di-(2,2')-methylene-3,4,6-Trichlorophenol-3,4,6'- molecules, and the products of the reaction are nickel trichlorophenate '6CHOH dimethylene bisphenolate and a Group a metal halide. A 8 grams (1.2 g atom) of lithium was added to a flask con direct reaction does not readily occur between nickel dihalide taining 1,500 milliliters of absolute methanol under a nitrogen and methylene bisphenol because there is insufficient driving atmosphere producing a solution of lithium methoxide. The force for this reaction. solution of lithium methoxide was refluxed at 65 C. and dur The desired reactions do not occur when attempted in aque ing this operation 488 grams (1.2 moles) of hexachlorophene ous solution. It has been found, for example, that, in aqueous 10 was added. This mixture was refluxed at 65 C. for 0.5 hour solution, precipitation of hexachlorophene occurs if the pH of and then a solution of 186 grams (0.6 mole) of anhydrous the solution falls below approximately 8. On the other hand, nickel bromide. EGDE complex in 600 milliliters of methanol when the pH of the solution is raised to keep hexachlorophene was added. The hot (55 C.) yellow-green reaction mixture in solution, nickel is formed and the desired 15 was then reduced to a volume of about 1.5 liters and then product, nickel hexachlorophenate, is not achieved. Ac cooled by immersing the flask in an ice/salt mixture. The cordingly, care must be taken to assure that the reactions are resulting light green, finely crystalline product which carried out under nonaqueous conditions. precipitated was filtered off, rinsed twice with cold (25°. C.) After the reaction, the resultant fluid mixture is concen anhydrous methanol and dried in a slow stream of dry trated by evaporation of methanol, and then cooled to 20 nitrogen. precipitate the crystalline product which can then be The product and two subsequent crops of crystals obtained separated from the remaining fluid by filtration. The crystal from the mother liquor totaled 466 grams (73% of theory line material obtained is then rinsed in anhydrous alcohol to based on CHCl2NiOo). The of the com remove impurities and alcohol-soluble byproducts, and dried pound (samples inserted at 105 C.) was 115-118° C., at under anhydrous conditions, e.g., dry nitrogen, to avoid possi 25 which temperature the compound decomposed. ble contamination with water. Drying may also be accom The calculated analysis for CshClNiOo, the empirical plished under vacuum, but in that case, the temperature formula for nickel hexachlorophenate '6CHOH, was as fol should be no higher than 26 C. to minimize loss of the lows: 36.16% carbon; 3.22% hydrogen; 40.03% chlorine; methanol of crystallization. 5.52% nickel. The calculated loss in weight upon removal of The use of the nickel compounds as light stabilizers for vinyl 30 six equivalents of methanol was 18.43%. The observed loss, on polymers such as polyvinylchloride, calls for mixing the nickel drying the compound for 4 hours at 110 C. in vacuum, was compounds with the polymer, for example, in a small but ef 18.09%. The calculated analysis for the residue after removal fective proportion of up to 10 parts by weight of compound, of methanol was: 35.87% carbon; 1.16% hydrogen; 48.87% e.g., 1 part by weight of compound per 100 parts by weight of chlorine; 6.74% nickel. The observed analysis of the residue the polymer, and with other necessary ingredients, at a tem 35 was: 36.07% carbon; 1.20% hydrogen; 48.26% chlorine; perature from about 75 F. to 285 F., until the powder mix 6.78% nickel. The melting point of the residue was 163°C., at ture is well blended and then, after cooling, extruding the which temperature it decomposed. The reactions are believed powder mixture or otherwise processing it to final form. to take place as follows: Ordinarily, a minimum of at least 0.25 part by weight of compound, per 100 parts by weight of polymer is required to 40 effect a substantial degree of stabilization. A highly satisfacto (1) 2Li + 2CH3OH - 2CH3OLi -- H, T ry addition is about 1 part by weight of compound, per 100 (2) Ho (pH parts by weight of polymer. This treated polymer is charac terized by a substantial ability to resist degradation upon expo CHO Li + Cl- Y-CH,- Cl sure to natural or artificial light for and extended period. 45 , --- In order to give those skilled in the art a better understand -C Cl ing of the invention, particularly the preparation of com C Cl pounds in accordance with the invention, the following illus HO OLi trative example is given: 50 - CH- -Cl -- CHOH EXAMPLE -C Cl 55 Preparation of Nickel Bromide Dimethoxyethanate Cl (Nickel Bromide:EGDE Complex) (3) Hip-N-pl. 3.5 liters of peroxide-free ethylene-glycol dimethylether 2 Cl- CH--- -Cl (monoglyme) and 600 grams (2.36 moles) of nickel bromide 60 - NiBr2 --> dihydrate were vigorously stirred and heated at reflux tem -Cl C perature (80 C.) for approximately 30 hours in a 5 liter round bottom Morton flask with a flange neck. The flanged cap was C Cl equipped with a suitable stirrer, two Soxhlet extractors and Nickel hexachlorophenate appropriate condensers, and during refluxing it was necessary 65 O O-Ni O O to recharge the thimbles with fresh desiccant (Cah). The dehydration was followed by periodic Karl Fischer titrations. Cl- CH2- -Cl Cl --CE- -Cl When a titration indicated a water content <0.04 mg/ml. sol -- 2LBr. vent, the salmon pink granular nickel bromide complex was -Cl Cl - -Cl Cl filtered off under nitrogen, and dried under nitrogen, with the - 70 intermittent application of a vacuum. The yield (740 grams, Cl Cl Cl Cl 2.4 moles) was quantitative. The calculated analysis for (4) NiBr CHOCH2CH2OCH3, the empirical formula for Nickel hexachlorophenate -- 6CH3OH --> nickel bromide dimethoxyethanate, was as follows: 15.5% nickel hexachlorophenate-6CH3OH carbon; 3.27% hydrogen; 51.78% bromine; 19.02% nickel; 75 balance oxygen. The observed analysis was 15.78% carbon; Hexamethanol nickel hexachlorophenate may also be 3.26% hydrogen; 51.97% bromine; 19.25% nickel; balance prepared from monogylme-complexed nickel chloride. How oxygen. ever, the bromide is preferred since the byproduct, lithium

6.458 tity A r - 3,627,798 S 6 bromide, has a higher in the methanol solvent reac Although the present invention has been described in con tion medium, and thus contamination of the product with lithi junction with preferred embodiments, it is to be understood um salts is minimized. Further, an anhydrous solution of that modifications and variations may be resorted to without nickel halide in a mixture of ethyl alcohol and ethyl formate is departing from the spirit and scope of the invention as those also satisfactory for the preparation of nickel hex 5 skilled in the art will readily understand. Such modifications achlorophenate. Such nickel halide complex is prepared by and variations are considered to be within the purview and reacting a hydrated nickel halide with triethyl orthoformate. A scope of the invention and appended claims. reaction of the following type is believed to take place: claim: 1. The process for preparing nickel hexachlorophenate O which comprises the steps of, CHOH a. reacting in an essentially nonaqueous solvent selected NiCl2.H.0+2HC(OCH) from the group consisting of methanol, ethanol, propanol, isopropanol, N-butanol, isobutanol, sec-butanol, acetone, NiCl-CHOH+2CHOC(O) H tetrahydrofuran, dimethoxyethane and dimethylforma 5 mide, hexachlorophene having the formula, The nickel halide solution thus obtained may then be reacted with a Group a metal methylene bisphenolate as described Ho ph above to produce the desired end product. Nickel hexaclorophenate (Compound 1 ) was evaluated as Cl- -CH- -Cl a light stabilizer by incorporation in polyvinylchloride (PVC) 20 film samples. In preparing the PVC film, nickel hex -Cl Ci achlorophenate '6CHOH was added in the amount of 1 part Cl Cl by weight of the nickel compound to 100 parts by weight of the PVC powder in a dry mixing head of the Brabender Plasto 25 with a Group Ia metal alkoxide, the reactants being em graph sigma blade mixer. The mixture was heated to 200 F. ployed in amounts such that the ratio of the Group Ia during mixing and then the temperature was raised to 230 F., metal ions to the CH bridging group of the hex and the mixture was heated for additional 10 minutes. At this achlorophene is essentially 1:1; point, 50 parts of dioctyl phthalate, a plasticizer, and two parts b. reacting an essentially anhydrous nickel halide with the of a gylceride lubricant (Glycoluble RP) were added. The 30 reaction product of step (a), the amount of nickel halide introduced being such that the ratio of nickel ions to the batch was dry blended for 45 minutes at 260 F. to 280 F., CH, bridging groups in solution is essentially 1:2; and and then cooled. The blended powder was then transferred to c. precipitating the resulting nickel hexachlorophenate. an extruder hopper and fed into the extruder screw. The ex 2. The process of claim wherein the solvent is methanol. trusion was carried out at a temperature of 300 F. and a 2 3. The process of claim 1 wherein the solvent is methanol inch wide by 0.01 inch thick film was extruded. The film was 35 and the essentially anhydrous nickel halide is selected from cut into about 9 inch lengths which were clamped in suitable the group consisting of a nickel halide dimethoxeythanate holders under slight tension with about 8% inches exposed for complex and an anhydrous solution of nickel halide in a mix weathering. Film holders were provided with PVC film sam ture of ethyl formate and ethyl alcohol. ples incorporating the stabilizing nickel compound of the in 40 4. The process of claim 1 wherein the metal alkoxide reac vention as well as with uninhibited PVC film samples (blanks). tant is the reaction product of a Group a metal selected from The PVC film samples were exposed in a carbon arc illu the group consisting of lithium, sodium and potassium, and an minated weatherometer to provide accelerated weathering alcohol selected from the group consisting of methanol, conditions. The cycle time on accelerated weathering was 102 ethanol, isopropanol, n-butanol, isobutanol and sec-butanol. minutes of simulated sunshine (carbon arc illumination) fol 45 5. The process of claim 3 wherein the Group Ia metal alkox lowed by 18 minutes of simulated sunshine and rain (water ide reactant is the reaction product of a Group Ia metal spray). The results obtained are set forth in the following ta selected from the group consisting of lithium, sodium and ble: potassium, and an alcohol selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, isobu 50 tanol and sec-butanol. Film Samples Hours to Failure Type of Failure 6. The process of claim 5 wherein the solvent is methanol. Blank A 230 Brittle, Black 7. The process of claim 1 wherein the Group a metal alkox Blank B 234 Brittle, Black ide reactant is the reaction product of lithium and methanol. Blank C 270 Brittle, Black 8. The process of claim 7 wherein the solvent is methanol. Blank) 229 Brittle, Black 55 9. The process of claim 1 wherein the Group a metal alkox Compound 1 908 Brittle (No ide reactant is lithium methoxide and the essentially an discoloration) hydrous nickel halide is the reaction product of nickel bro mide dihydrate and ethylene-glycol dimethylether. 10. A process of preparing nickel hexachlorophenate '6CH It is seen that the uninhibited samples (blanks) exposed 60 OH under anhydrous conditions which comprises first react failed consistently at less than 300 hours. Nickel hex ing, in methanol, hexachlorophene and lithium methoxide, achlorophenate '6CHOH clearly stabilizes polyvinylchloride then introducing as a reactant nickel bromide dimethox against degradation upon exposure to light, time to failure yethanate, and thereafter precipitating nickel hex being more than three times that of the uninhibited samples. achlorophenate '6CHOH. Similar results are obtained using nickel hexachlorophenate, 65 11. A nickel compound having the general formula, without associated methanol since, in any case, the methanol is driven off during the heat mixing process. An efficient and relatively simple process has thus been HO O - No OH presented for the preparation of nickel hexachlorophenate C1 CH, C1 C1 CH, C1 and usefulness of this nickel compound has been demon 70 strated as a light-stabilizing additive for vinyl polymers. It is contemplated that nickel compounds described herein O O N/ N/ may have application, not only as stabilizing additives for vinyl Yo C Yo c? polymers, but for polyolefins as well, e.g., polyethylene and Cl Cl C Cl polypropylene. 75 it k

6459 - or UNITED STATESsigner starts: PATENT OFFICE (5/69) CERTIFICATE OF CORRECTION Patent No. 3, 627,798 Dated December l4, 1971. . Inventor(s) LAIRD GORDON LINDSAY WARD It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: - -

Col. 6, line 5 of claim 4, after "ethanol," insert --propanol, --.

Signed and sealed this 29th day of October 1974.

(SEAL) Attest : McCOY M. GIBSON. J.R. C. MARSHALL DANN Attesting Officer Commissioner of Patents