Document O3qyDRRx7vY1bVoOv709dGGXv

CCs Dr. j. B, Booge-Pigts Mr* I. J, Krehma-Pigts .-Wilm. Dr. C. M. Olson Dr* B* J, Fahl Dr* C. 0. Bostwick Dr. H. C. -Gulle&ge Dr. W. W. Riches Dr. 0, M, Cook Dr. E 9 K Ott Dr. J* K. Sudor Mr. F. W. Iane-Newporfc :Dr. H* C, Brill-Mewport Experimental Station August 27. 1953 DR. 0. R* SEIDEL PIGMEKTS XEPiURTMEKT EXPERIMENTAL STATIQM lATIOmL LEAD * 3 RESEARCH 01 TITAHIUM ORGAHICS The writer attended the Cordon conference on Organic Coatings at which two papers were presented by representatives from National Lead Company. It is apparent that they have done con siderable work and that we have real competition from them in this field. In order to acquaint our staff with their work, the writer took extensive notes on both talks and is incorporating in this letter the major points. Dr. D. F, Hannan gave a talk entitled, "The Chemistry of Titanium Organic Compounds," Dr. Herman is the man who first isolated a compound containing a titanium carbon bond but his talk was principally about titanium esters. In private conversation Dr. Herman said that the TI-C compounds which he had made so far were all too unstable to have practical use. He described several complexes between butyl titanate and ethylene diamine, ammonia, and HC1 and stated that these compounds were somewhat less reactive than the simple esters. He also described association of titanium esters which followed closely our concept of this. He described four reactions of titanium esters. Reaction, with hydrochloric acid was stated to proceed as follows: Ti(QBu)4 / HC1 (Bu O>3 T1C1 / BuGH. The hydrolysis of TBT was stated to proceed rapidly but did not go to completion. The following table was given to show the extent of hydrolysis: Moles Moles HgO RO per* TBT/Hq Q Unreacted Titanium Remaining *00 a.35 .02 1.95 1.2 1,1 N35477 As an Indication of difference in hydrolysis rates, laanetron readings were made on solutions of various titanium esters with water added and these are given in Figure 1 attached in the appendix. As expected, the lower titanates hydrolyze much faster than do the higher ones. The hydrolysis of mixed titanates was stated to proceed as ex pected, the lower boiling alcohol being removed first. Thus, the reaction of dibutyl, dioctyl titanate and 1 mole water would produce condensed dioctyl titanate and 2 moles of butanol. ' The reaction with polyols was described briefly and it was stated that depending upon the proportion of TBT to polyol, materials ranging from fluids, to putties, to solids could be produced. An interesting table ms given on the reaction of triethanol amine with TBS in which the butanol was stripped off on a steam bath under vacuum. These results were as follows t Mole Ratio TEA-TBT BuO Replaced Appearance Water Solubility 0.66 1 1.33 1.5 1.96 2.76. 3*68 h.o Very viscous Semi solid Glassy Glassy Partly soluble Partly soluble Soluble Soluble The acylation reaction was described with results analogous to our work. An interesting concept of the mechanism involved was presented, however, in which it was postulated that the mechanism with acetic acid, for example, is as followsi (BuO)^ Ti / HOAc ^ (Bu G)3 Ti (OAc) / BuOH BuOH / HOAc ^ BuOAc / HgO (Bu O)3 Ti (OAc) / Hg0. OAC t -TiO- OBu / SBuOH ^ As proof of this mechanism Dr. Herman stated that they had actually been able to distill off some water from the reaction mixture. Although national Lead did not talk much, about the acylates, they rather obviously are receiving considerable attention. They have made titanium methacrylate (which we have failed to do) and stated that it polymerized by a normal free radical mechanism. DUP030003552 4 In private conversation with the writer Dr. Herman stated that National Lead has a new process for producing titanium esters. This involves reaction of TICI4 with alcohol in a liquid asanonia medium. The co-product ammonium chloride is soluble in liquid ammonia and the reaction mixture separates as two liquid layers, the lower layer being TBT. These are merely' separated and the THE distilled. This has the advantage over our process of avoiding the use of large quantities of solvents and may be more economical. Dr. H. H. Beacham gave a paper on the use of titanium organic compounds in coatings. He gave numerous examples including many vis cosity curves on dopes made from TBS and ethyl cellulose, nitrocellulose, cellulose acetate, alkyds, phenolics, and epoxy resins. He also stated that they had worked with vinyl acetate, vinyl acetate-chloride, vinyl maleates, vinyl ethers, urea-forsaldehyde, melamlne^formaldehyde, and , silicoses. In order to minimise gel formtlon they have used a number m of tricks, one of which is the use of butanol as a solvent which tends *\ to reverse the reaction (if TBS is used). Figure 2 shows a graph on this effect with ethyl cellulose. The effect of various alcohols as co-solvents was also described. This is also the system with ethyl cellulose using a fifty-fifty TBT-ethyl cellulose mixture. The solvent was in each case 8c$ bensene with 20$ of various alcohols added. Ke>suits were as follows? Alcohol Viscosity, cos MeOH BtOH iso-PrOH n-BuOH 1-BuOH sec-BuOH t-BuOH ethyl-lactate ethylene glycol gel gel p. gel 275 300 370 400 225-- 250 ~ It may be seen from this that ethyl lactate and ethylene glycol were more effective In preventing crosslinking than were the simple alcohols. This is to be expected since these materials can form chelates. It should be very useful for us to incorporate such ligands in our cellulose acetate dopes, Amino alcohols and^-diketones as well as simple amines were also used. Figure 3 shows the effect of trletbylamlne on the viscosity of TBS ethyl cellulose solutions. The effect of ethyl "lactate and ethyl aeetoacetate on the viscosity of cellulose acetate solutions was given in Figure 4, The properties of ethyl cellulose and TBT in fifty-fifty mixtures were listed. These showed that the film were harder and more resistant to H01 and various solvents. The material was stated to be water white. DUP030003553 >4 A very- hard film was produced from the following fonsulatlon; 5 parts of Nitrocellulose 40 parts of Ethl lactate 4o parts of Butanol 3 parts of Plasticizing Castor Oil Alkyd 5 parts of Tetra~n~Butyl Tltanate [TBS) In this the plasticizer also yeasts and becomes a part of the film, Shis particular formulation has too low a solid content to be practical. The following results were obtained by adding TBT to a soy modified al&yd; Alkyd Color Tack-free Hardness Air dried 6 days >0 25* - 6 hrs. 100* - 1/2 hr SJaOH 2 xylol 2 hrs. Yellow 24 hrs. 10 4 (blush) 4 (wrinkle) very soft very soft Yellow 2 hrs.. 18. 16 1105' 12 With phenolic the following results were obtained? Hardness Air dried Mineral spirits 0.5# NaOH Dielectric Strength Phenolic 15 dissolved badly swollen 1500 Phenolic Mjm 41 15 26 2400 Figure 5 shows the effect of triethanol amine tltanate added to phenolic on the dielectric strength of the coating. With epoxy resins it was stated that these materials were difficult to prevent from gelling but that this could be done with /^-diketonesj triethanol amine* or diamine-TBI complexes. Since diamines are normally added to epoxy resins as a curing catalyst, these were particularly attractive. The formulation which they reported to be good was as follows! 100 parts of Epon 1007 100 paras of Oiacetone Alcohol 100 parts of Ethyl Cellosolve 2.5 parts of TBT 2.5 parts of-amino Ethyl Ethanol Amine DUP030003554 `i 5 Another formulation ms made up in two parts which were merely mixed prior to application. These were as follows: Part A. 100 parts of Epon 1007 100 parts of BLacetone Alcohol 100 parts of Ethyl CeXlosolve Part B. /"~6.5 parts of TBT f 46.3 parts of Butanol j 6.5 parts of Ethylene Diamine These two solutions were mixed Just before curing and cured at 80C. The resulting films'were hard and solvent resistant . JHHscdb DUP030003555 Lumetron Appendix Figure 1 Figure 2 DUP030003556 V ise* Figure 3 HI I wnWTiWU.i--IIMnfflgii V ise s V ise,, 5P % me 100 DUP030003557 Figure $ 200QJ PhmJit "t /0% TAT B ieleefcrie S trength 1200J TT 4 Baling time, hours 7 8 DUP030003558