, 2,883,348 United States Patent Office Patented Apr. 21, 1959 1. 2 linkage. Thus, the diepoxide of glycidyl 3,4-epoxybutyr ate or diglycidyl phthalate, diglycidyl maleate, diglyc 2,883,348 idyl succinate or the di- or polyepoxy compounds ob PRODUCTION OF TTANUM ESTERS tained by condensation of bis phenol A (condensation Alphonse Pechukas, Pittsfield, Mass., assignor to Colum product of acetone with phenol) with epichlorohydrin, or bia-Southern Chemical Corporation, Allegheny County, the phenyl polyglycidyl ethers and the polyglycidyl ethers Pa., a corporation of Delaware of bis phenol A, or the like also may be used to produce resinous products in accordance with the present invention. No Drawing. Application December 16, 1954 The resins herein contemplated may be prepared by re Serial No. 475,829 10 action of titanium tetrahalide, such as titanium tetra chloride, with the epoxide. The reaction apparently pro 2 Claims. (C. 260-2) ceeds according to the following equation: O O This invention relates to a novel resinous composition of matter. According to the present invention, it has 15 TiCl, + -4 S-X-1 Sq- -md been found that a novel resinous product can be pre pared by reacting together a titanium tetrahalide and a -t-o-c-d-x-0-0-0-t- polyepoxide. By the term "polyepoxide' is meant a com bi by pound which contains two or more epoxy groups in which and/or the oxygen atoms of the epoxy groups are linked to ad 20 jacent carbon atoms and which therefore contain at least - i-o-c-x-di-O-t- b. two of the groups: C-Cl (-C) O / o, and/or -4 Sq- or -4 Sp-- 25 –t-o-c-x-b-c-o-t- in which the two carbon atoms to which the oxygen -(-C) by atom is linked are linked to groups other than acidic OH groups. These epoxides are referred to hereinafter where X is the group which links the epoxy groups to as 1,2-epoxides. 30 gether. Thus, the overall reaction proceeds according to The resins thus obtained may be regarded as resinous the general equation: esters of orthotitanic acid and glycols having a halogen atom or a chlorine atom linked directly to a carbon atom -C immediately adjacent to each of the alcoholic . -(-C) 35 2 Co -- TiCl, -) -TiCl --OH - C J s groups of the glycol. Thus, the resinous esters have the where n is a small whole number not less than 2 nor Structure: more than 4, m is equal to 4-in, and where 40 ----------------by bi' ' ' ) by and -- -o-c-x-E-O-t- O-(-x-di-O- 45 represents the epoxy groups of the epoxy compound. According to a further embodiment, polyhalotitanates --Cl --ol --Cl --CI having the structure: The epoxides herein contemplated may be prepared (R-OlTiCl by subjecting compounds which contain two or more 50 where R is a radical of a monohydric alcohol ROH and ethylenically unsaturated groups to epoxidation under con ditions such as to epoxidize at least two of the unsaturated m plus n equals 4, m being 1 or 2 and n being 2 or 3, groups. Since the epoxides are conventionally prepared may be reacted with polyepoxides to produce resinous from unsaturated compounds, it is convenient to desig products. nate the epoxides in terms of the unsaturated compounds According to a further embodiment of the invention, from which they have been or can be derived. For ex 55 mixed polyepoxides can be prepared using partial esters ample, since the compound of titanium tetrachloride having the formula: IR-Olm,TiCl where R is a monovalent radical of the titanate ester, 60 usually derived from a monohydric alcohol ROH. and the sum of m plus n is 4, m being 1 or 2 and n being can be derived from butadiene-1,3, it is conventionally 2 or 3. Normally, R contains no more than 10 carbon known as butadiene epoxide. atoms. The resins herein contemplated may be prepared from Saturated esters which may be used according to this various polyepoxides such as the di- or polyepoxides ob 65 embodiment may include: 2-chloroethyl titanium trichlo tained from butadiene-1,3, isoprene, cyclopentadiene, buta ride, ethyl titanium trichloride, n-propyl titanium trichlo diene dimer, divinyl benzene, dicyclopentadiene or poly ride, stearyl titanium trichloride, phenyl titanium trichlo cyclopentadiene. In most cases the two epoxy groups are ride, bis(2-chloroethyl) titanium dichloride, diethyl ti linked together through a carbon chain. Such com tanium trichloride, dibutyl titanium dichloride, ethyl 2 pounds produce materials which are less subject to hydrol 70 chloroethyl titanium dichloride, distearyl titanium dichlo ysis. However, it is also possible to make use of epoxides ride, diphenyl titanium dichloride, and the corresponding in which the epoxy groups are separated by an ester bromides, iodides, and fluorides, as well as the corre 2,883,348 3 4. sponding compounds in which hydrogen atoms are sub proportion of approximately 0.1 to 5 percent by weight stituted by halogen, NO3, alkoxy groups, phenyl groups, of the catalyst, based upon the resin, and heating the and the like. product at a convenient temperature, depending upon the According to a particularly advantageous embodiment effective temperature at which the peroxide functions. of the invention, a resinous material which is further poly For example, with benzoyl peroxide, heating can be con merizable by virtue of the unsaturated groups can be pro ducted at a temperature ranging from 70 up to 105 C. duced using chlorotitanates of unsaturated alcohols. These With tertiary butyl peroxide, a lower temperature can include chlorotitanates having the formula: be used. With acetone peroxide, higher temperatures must be used. (R-O--TiCl, 0 The above described resins may be prepared in ad where m is 1 or 2, n is 2 or 3, and R1 is an unsaturated mixture with other resins and resin-forming materials. monovalent radical, preferably containing no more than Notably, the unsaturated two-dimensional unsaturated 10 carbon atoms and containing the polymerizable group resins derived from the unsaturated dihalotitanates and C=C. Thus, as herein contemplated, R may be an allyl, diepoxides may be mixed with polymerizable unsaturated 2-chloroallyl, methallyl, crotyl, cinnamyl, oleyl, linoleyl, 5 liquids containing a polymerizable aliphatically unsatu cyclopentadienyl or propargyl group, or the like. Thus, rated carbon-carbon group, such as styrene, methyl the compounds which may be reacted with diepoxides in methacrylate, acrylonitrile, diallyl phthalate, propylene accordance with this embodiment of the invention include: glycol maleate or the like, and the mixture polymerized dially titanium dichloride, allyl titanium trichloride, by heating with peroxide under ultraviolet light and/or oleyl titanium trichloride, 2-chloro 3,4-butenyl titanium 20 in air to form copolymers. The other titanium resins de trichloride, bis(2-chloroallyl) titanium dichloride, allyl 2 scribed above may be copolymerized in a similar way. chloroethyl titanium dichloride, cinnamyl 2-chloroethyl The resins herein described may be used to impregnate titanium dichloride, and the corresponding other halides. various types of fibrous materials as, for example, fibrous The terms "polyhalotitanate” and "polychlorotitanate,” glass cloth, asbestos, cotton fabrics, and the like, and, as used herein, are intended to include titanium tetra 25 after impregnation, the sheets may be laminated and halide and titanium tetrachloride, respectively, as well shaped to a desired contour and further polymerized. as the organic derivatives thereof, in which one or two Thus, the herein contemplated resins may be used gen of the halogen or chlorine atoms are replaced by the erally in the same processes which are conventionally in group OR where R is a monovalent organic radical. The use in the polymerization of glycol phthalate-maleate terms "organic halotitanate' and "organic chloro 30 products such as are described in U.S. Patent No. titanate' mean the compounds in which the halogen or 2,593,787, granted April 22, 1952. These resins in their chlorine atoms of titanium tetrachloride are replaced by partially or completely cured state also may be used as OR groups where R is a monovalent organic group. coating agents for coating metal, wood, fabric or the Thus, the prefix "poly” refers to the halogen or chlorine like, and as modifiers for other resins. atoms, i.e., the compounds contain two or more chlorine 35 The following examples are illustrative: or halogen atoms attached directly to a titanium atom. The proportion of titanium chloride to polyepoxide Example I should, for most cases, be in the proportion of about A solution of one volume of titanium tetrachloride 0.25 to 2 chlorine or like halogen atoms attached di to two volumes of methylene chloride is cooled to 5° C. rectly to the titanium atom of the titanium chloride per 40 in dry air. Ethylene oxide in the proportion of 1.92 epoxy group of the polyepoxide. Best results are parts by weight to 8.65 parts by weight of titanium achieved when the ratio of such chloro or halo groups tetrachloride is added dropwise to the solution and the to epoxy groups is substantially one plus or minus 25 solution is stirred vigorously while maintaining the solu percent. tion temperature at about 5 C. The production of these esters is accomplished by mix 45 The resulting yellow solution containing 2-chloroethyl ing the epoxide with the titanium tetrachloride or other titanium trichloride is then allowed to warm to room titanium tetrahalide at a temperature usually below 25 temperature for several hours. Thereafter, it is cooled C., preferably below 10° C. Inert solvents, such as to 5 C. and 3.2 parts by weight of 1,2-epoxybutene-3, carbon tetrachloride or methylene chloride or other sub stantially inert chlorohydrocarbon solvents, are normal 50 dissolved in 10 volumes of methylene chloride per 3.7 ly used in order to prevent overheating and in order to volumes of epoxybutene, is added dropwise with cool prevent more ready control of the reaction.