United States Patent to 11, 4,020,010 Vogt Et Al
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United States Patent to 11, 4,020,010 Vogt et al. 45 Apr. 26, 1977 54) TIN TITANIUM COMPLEXES As (56) References Cited ESTERIFICATION/TRANSESTERIFICA. TON CATALYSTS UNITED STATES PATENTS 3,056,818 10/1962 Werber .......................... 252/431 C (75) Inventors: Herwart C. Vogt, Grosse Ile; Manher 3,714,234 i? 1973 White ............................ 252/431 R 3,716,523 2/1973 Cook ...... ... 260/75 M Parekh, Woodhaven; John T. Patton, Jr., Wyandotte, all of Mich. 3,884,832 5/1975 Pullukat ......................... 252/43 R Primary Examiner-Winston A. Douglas (73) Assignee: BASF Wyandotte Corporation, Assistant Examiner-John F. Niebling Wyandotte, Mich. Attorney, Agent, or Firm-Norbert M. Lisicki; Bernhard R. Swick; Robert E. Dunn 22) Filed: Dec. 29, 1975 57 ABSTRACT (21) Appl. No.: 644,357 Complexes of stannous carboxylate and tetraalkyl tita nate are effective esterification and transesterification (52) U.S. C. ........................ 252/431 C; 252/431 R catalysts. (51) int. C.’............................................ B01J 31/2 (58) Field of Search .................... 252/431 R, 431 C 7 Claims, No Drawings 4,020,010 1. 2 tetraaryl titanate will result in complexes which are TIN TITANIUM COMPLEXES AS more efficient than the individual metal components as ESTERIFICATION/TRANSESTERIFICATION esterification/transesterification catalysts. The com CATALYSTS plexes may be used for any type of mono- or polycar boxylic acid and anhydride to be esterified with any BACKGROUND OF THE INVENTION suitable hydroxyl containing material. 1. Field of the Invention This invention relates to the preparation of tin DESCRIPTION OF THE PREFERRED titanium complexes. More specifically, this invention EMBODIMENTS relates to a process of preparing esters and polyesters in 10 The tin-titanium complex may be described by the an improved manner by using these novel complexes as following general formula: esterification/transesterification catalysts. 2. Prior Art The preparation of esters and polyesters is well known in the art. These materials are prepared by es 15 terifying mono- and/or polyhydric alcohols with mono Ti(OR), Sn OCR' U , and/or polycarboxylic acids. In many instances it is desirable to prepare such esters or polyesters having a very low acid number, i.e., less than two. However, the wherein R is a radical selected from the group consist attainment of an ester or polyester having a low acid 20 ing of an aliphatic radical having from 1 to 18 carbon number is extremely difficult to achieve. For example, atoms, an alicyclic radical having between l and 3 during the last stage of the esterification of the reac rings, between 5 and 6 carbon atoms per ring and be tion, the reaction proceeds extremely slowly and hence tween 5 and 18 carbon atoms per molecule, and an in order to reduce the acid value it is necessary to heat aromatic radical having between l and 3 rings and for a lengthy period of time at relatively high tempera 25 between 6 and 18 carbon atoms per molecule, R' is an tures. This, in many instances, tends to bring about organic radical having from 1 to 18 carbon atoms and formation of a darkened ester or polyester which is x and y are whole numbers in the ratio of 1:1 to 1:8. unsuitable for further use. Various attempts have been The complexes of this invention are prepared by made to reduce the time of the esterification reaction. reacting together, under anhydrous conditions, and in For instance, British Pat. No. 792,011 describes the use 30 the absence of air, at room temperature, the desired of iron, cadmium, cobalt, lead, zinc, antimony and concentration of stannous carboxylates with the de manganese in the form of the metal, its oxide or its salt sired amount of tetraalkyl or tetraaryl titanate. It may with a bibasic acid. Other catalyst types are more reac also be desired to heat the reactants if shorter reaction tive. For example, stannous compounds of the type times are desired and to assure completeness of reac Sn(OOCR), wherein R is selected from the group con 35 tion. The reaction of these two clear liquids is often sisting of saturated and unsaturated aliphatic hydrocar accompanied by orange, light yellow, or red color for bon constituents having from about 7 to about 17 car mation and the liberation of heat. Sometimes it is desir bon atoms have been described in U.S. Pat. No. able to carry out this preparation in a suitable inert 3,162,616 and U.S. Pat. No. 3,716,523. Organo tita solvent to permit easier handling of the complex. Sol nium or organo zirconium compounds have been dis 40 vents such as anhydrous xylene may be employed. In closed by U.S. Pat. No. 3,056,818 as being suitable as addition to the color formation and heat evolution esterification catalysts. Titanium compounds are often which indicate a new complex compound has been insoluble in the product and must be removed by filtra formed, it has been found that the tin-titanium complex tion or other tedious procedures. The technical litera has improved hydrolytic stability. It is well known that ture also notes that esterification is usually effected by 45 stannous salts of organic acids and titanium alkylates refluxing the acid and alcohol with a small amount of are very susceptible to trace amounts of moisture acid catalyst such as sulfuric acid, hydrochloric acid, which leads to rapid hydrolysis, catalyst deactivation, and sulfonic acids or boron trifluoride. Acid catalyst and often solid formation. For example, tetrabutyl tita often causes color formation and must be removed to nate is immediately decomposed by water forming insure a stable low acid number product. 50 titanic acid. Atmospheric moisture may produce high Esters may also be prepared by transesterification molecular weight condensation products which pro reactions. These transesterification reactions include ceed until titanium dioxide or the hydrous titanium the reactions between two esters to yield two new es dioxide is formed. Stannous octoate undergoes similar ters or the reaction between an ester and an alcohol to hydrolysis type reactions with water and precautions form a new ester and liberate an alcohol. Included also 55 must be taken to prevent the destruction of the cata are the transesterification reactions where the compo lyst. nents of the esters involved are polyhydroxy alcohols Any suitable stannous salt of a carboxylic acid may and polybasic acids. These reactions may, in some be used to prepare the complex. These may be de instances, be catalyzed by those substances which are scribed by the following formula: employed for the esterification procedure. We have 60 discovered that polyesters having an acid number less Sn(OOCR) than two can be prepared in relatively short period of time with tin-titanium catalyst complexes employing wherein R is a saturated or unsaturated, straight or either esterification or transesterification procedures. branched chain, aliphatic or aromatic substituent hav 65 ing from about 1 to about 18 carbon atoms in its chain. SUMMARY OF THE INVENTION Stannous octoate and stannous oleate are preferred. It has been discovered that certain unique combina Other suitable stannous salts are stannous naphthenate, tions between a tin carboxylate and a tetraalkyl or stannous acetate, stannous butyrate, stannous ethyl 4,020,010 3 4 hexoate, stannous laurate, stannous palmitate, and removal at the later stages of esterification, a vacuum StanOuS Stearate. of 0.1-100 mm Hg is employed. The time of reaction The titanium compounds which are employed can be will depend on the reactivity of the reactants, the stoi represented by the general formula: chiometry, temperature, and pressure employed in the 5 reaction, the molecular weight of the resulting polyes Ti(OR) ter, the rapidity with which the water of esterification is removed, and the activity of the catalyst employed, if wherein R is a radical selected from the group consist any. ing of an aliphatic radical having from 1 to 18 carbon Any mono- or polycarboxylic acid and anhydrides atoms, an alicyclic radical having between l and 3 () thereof may be employed for the preparation of esters. rings, between 5 and 6 carbon atoms per ring, and Thus, the acids undergoing esterification can be ali between 5 and 18 carbon atoms per molecule, and an phatic, cycloaliphatic or aromatic and they can be aromatic radical having between l and 3 rings and substituted or unsubstituted. Among the acids which between 6 and 8 carbon atoms, per molecule. may be employed include acetic, acrylic, propionic, Examples of these compounds include tetramethyl propiolic, isobutyric, methacrylic, n-butyric, pivalic, titanate, tetraethyl titanate, tetraally titanate, tetrapro ethylmethylacetic, isovaleric, chloroacetic, o-chloro pyl titanate, tetraisopropyl titanate, tetrabutyl titanate, propionic, n-valeric, dichloroacetic, diethylacetic, tetraisobutyl titanate, tetraamyl titanate, tetracyclo isocaproic, o-ethyl-n-butyric, methoxyacetic, n pentyl titanate, tetrahexyl titanate, tetracyclohexyl caproic, ethoxyacetic, bromoacetic, heptoic, o-ethyl-n- titanate, tetrabenzyl titanate, tetraoctyl titanate, tetrae () caproic, a-bromoisovaleric, hexahydrobenzoic, di thylhexyl titanate, tetranonyl titanate, tetradecyl tita bromoacetic, n-caprylic, a-phenylpropionic, un nate, and tetraoleyl titanate. decanoic, g-phenylpropionic, mesity lenic, tricarbally Mixed alkyl titanate compounds wouid include lic, o,6-dibromosuccinic, tartaric, 3,5-dinitrosalicyclic, trimethylbutyl titanate, dimethyldibutyl titanate, trie p-toluic, acetylenedicarboxylic,