Document Yj3LnBpGzMYGn8DOV7RMrBObV

Cross Reference:: punch Card Index 1810 / ' ``INOEXED'V*** <1 lwt=-......... '" m (OR ORCOIAIWi MRMORAIDCM REPORT 10. i&Sl MARSKAIi MORATORY October 23* 1952 . >v P10MBKTB DEPARTMENT - TXTAHUM 0R6A1ICS Introductions The Pigments Department has worked on tltaninm-organo compounds o t s p the past ten years# AM during this period# they have offered numerous samples to the p# & P. Department for valuation. These titanium organic compounds have comprised three types% (1) the titanium esters# Ti{0R)4# (2) the titanium aeylates 02GR ~ r n c r -i 2 1 r- R0 - no - Ra or HO - T10 - H 1 OR X ,, OH . ,, and (3) the titanium chelated esters# such as octylene glyeyl titanate and titanium glycolat. Host of our experimental work has been don with the titanium esters# particularly the lower esters,tetr&Iscpropyl f&" titanat (TFT) and tetra n~butyl titanat (TBT). Considerable experimental work has been done on the titanium aeylates# such I i? as titanium soy acylate# titanium linseed acylate and titanium stearate, gome work has also been don with the chelated esters. |; This experimental work has been done by many people in different groups in connection with specific problems. The purpose of this report is to summarise this work to date. Summary? The titanium*organo compounds have been tested for various purposes# the more, important of'which wares 1. As agents to Improve adhesion.. N35459 '> -2 * 2, As agents to produce inaolubillaatlon o p fast set. 3, As agents to redace blistering of house paint. 4, As constituents of house paints to improve durability characteristics. 5, As modifiers of aliyd resins. 6, As constituents of ''Duco* furniture sealers. T. As agents to reduce wrinkling, 8. As pigment dispersing agents. 9. As crosslinking agents for xw? and polyvinyl acetate plywood adhesives. 10. Miscellaneous applications. With the exceptions"-noted below, the results of this work have been negative, Hewburgh and Flint laboratories have also worked with the titanium organics, but so far have not found any practical uses for the. Following pigments Department's reccmendations, a con siderable amount of unsuccessful work was done with a X*2$ solution of tetraisopropyl iitanate in anhydrous isopropanol as an agent to Improve adhesion. The pigments Department now state that tetra, isopropyl titanate, used in this way, is not effective for this purpose unless the relative humidity at the time of application is below 4c$. Very recently, however, R. j, Sheppard has found that a solution of 4.5$ TFT and .$$ OA in toluene, applied as a wash coat over 64-1690 Sheet Metal primer or over 683-1196 Body surfscar, definitely improves the adhesion of the OA topcoat to these two undercoats. The improved adhesion has been spotty and further work is being done to establish the effect of humidity and other factors on the reproducibility of the results. Tetra n~butyl titanate is an effective fast setting agent when applied over a castor oil alkyd film, but the rapid hardening Is a surface effect only and through hardening is low at room temperatwo. However, this effect might be utilised in producing a fast setting printing Ink, where film thicknesses are of the order of ,1 mil. Xsopropoxy titanium stearate 1 the most effective agent so far found for reducing moisture migration in wood, isopropoxy titanium oleate Used as a primer on new wood reduces the blistering of #4o Outside white significantly. These exporimontal observations may eventually find some ooissereial utilisation, but It should b noted that there are other promising leads for reducing blistering of house paints. DUP030003445 3 Small percentages of tetrabutyl titanaie added to 93-00 Black definitely disproves the wrinkle resistance. Shis lead is still under active study* Action (!) F. Ik F.8s experimental work with the titanium organics* as outlined above, was reviewed with Messrs.. Seidel, Raslam and Brill of the Figments Department on October 2 at Marshall Laboratory. (2) At the October 2 meting* Dr. Brill was requested t give us, in writing, his best recomendation for overcoming the moisture sensitivity of tetralsopropyl titanat, so that this material can be used in a practical way as m adhesion improving agent* J. p. .sensattei will test these suggestions when they are received. (3) Following his encouraging initial results, R. j* Sheppard will establish the utility of TFT for improving the adhesion of ok topcoat t automotive undercoats. , (%) The use of TFT and T as insolubilizer# or fast setting agents for nitrocellulose, alkydo, pons* etc., utilising a double nozsle spray gun for miking the materials. Is being explored by s. Bochberg* ' (5) So Hochberg also plans to prepare a tltanated silicone in an effort to produce a silicone polymer which can be cured at lower temperatures. (6) R. A. laBerge will include the titanium acylstes in his future studies aimed at reducing blistering of outdoor house paints. (7) Mo other work with the titanium organics is planned, unless new ideas arise or are suggested by the Figments Department. Discussion* Chemistry of the Titanium organics The Titanium Raters The titanium esters f!{0B}a are characterised by rapid hydrolysis on exposure to water or moist air. The rate of hydrolysis varies with the size of the R group, but if R is small (k carbon .atoms or less), hydrolysis is extremely rapid* The end product of the hydrolysis is TiOg, but the reaction proceeds in steps, and products such as * (RO}3 T10 L (g r )3 R 9* OR *x DUP030003446 can also b obtained Another reaction of the titanium ester is ester interchange with alcohols* This proceeds rapidly at ordinary temperatures without catalyst, This reaction may he represented by the equations Si(9R)4 + %i8QB TiCOR* )j j t %EOH It is usually easy to convert.a titanium ester to a higher ester by distillation of the lower boiling HOH. Because of this reaction, the titanium esters can be used to crosslink polymers containing hydroxyl groups, such as nitrocellulose, polyvinyl butyral, epon resins and certain alkyds. These reactions are very rapid .even at room temperature, The lower titanium esters are liquids that are soluble 3.n alcohol., hesane and carbon tetrachloride* fetralsopropyi titanate boils at 232c* pilute solutions of TFT or TBT {% or less) applied as a thin film to a surface will hydrolyse to give a clear, continuous fIliST"provided the relative humidity is below 4og. At relative humidi%I@i^Mg^F^f^^*^SS5ol^m^""dFpowery deposits are obtained. Even at low relative humidities, the films are extremely brittle and will erase or powder unless the film thickness is of the order of *1 mil or less. The Titanium Acylates The titanium acylates are polymeric materials that have the general formulas r .ogcRi r R80 - T:!0 - R8 \ OR8 , X oon fj or HO - TIO 1 L OH J Among those that have been prepared are titanium stearate, titanium soy aeylate, titanium linseed eeylabe, titanium castor acylate and titanium eoeoanmt acylate.* These materials range from gummy to waxy solids, which soften and flow at temperatures below 1250* They are very soluble In non-polar solvents such as hydrocarbons and' carbon tetrachloride, and are completely insoluble in polar solvents, such as water and acetone-* Unlike the titanium esters, the titanium acylates .are reasonably water stable at room temperature, and alcoholysis only take place slowly at elevated temperatures. The soya and linseed titanium sseylatea dry much faster than the corresponding drying oils, but they give soft and very brittle films* The titanium acylatcs have been recommended as modi*, fiers of alkyds and other coatings and as pigment dispersing agents* DUP030003447 5 Specific .Evaluations $ ' .1. Aa Agents to Improve Adhesion , -T&traisopropyl tltarate,-applied from a .1-2$ solution ih anhydrous Isopropyl alcohol * was .specifically recommended by paints to 'painted surfaces. -ibis suggestion was first tested in I. 0, Jjlmperf *s group with Inconclusive or negative results, J, p. Semitfcei then conducted a careful series.of tests over olds glossy alkyd, -semi-allQrd and oleoresinous paints, using alkydj, semt-alkyd, and latex- paint m topcoat - with and without the TFT treatment, m all, 25 panels were prepared in this program, and a total of 4o tests for adhesion were made t o ? a period of one .month. . in every ease.- there was no significant improvement in ad hesion, as .a .result .of~t"Ee ifT treatment .'"''''Siii7tIItI,,lfiW'"d:.- from.August 2& to the air conditioned Marshall Laboratory, in.which the'uisaer-relative humidity is 45-70$. After this test program was completed, figments Department advised that Wf is not effective in 'improving adhesion, unless the relative humidity.is"4<j$.or less at the time, it is applied, obviously such a product isnot satisfactory for Trade gales use. figment Department realises, this now, and' are trying to overcame the moisture sensitivity of the TFT by addition of small amounts of linseed oil or other ,'raaterial, to a TFT solution In hexane. Such mixed solutions are effective -initially, but lose their effectiveness on aging, pigments Department are how attempting to improve stability on aging. In the .meantime, they are. no longer recowending 1*2$ TFT in.anhydrous ispropanol as a. JJliquid sandpaper" for Trade Sales use* Sine# the meeting With Figments'Department on October 8, r * J. Sheppard has just .recently obtained very promising initial results-with a dilute solution of TPT end.OA in toluene,-used aa a wash coat, to improve, the adhesion of o a topcoat to automotive undercoats. This work is being continued* The titanium ester and aeylafces have .also been tested for. improving adhesion"in the systems listed below, in this work, the .'titanium ester .(TFT or 1ST) a a 1-5$ .solution in anhydrous isopropanol, was usually used.as a wash coat direct to the substrate or`between coats of the paint system. The titanium acylates were'tested, by 1 adding them'to the topcoat, to the 'undercoat, or to both. (A) Oil to undercoat. Work dom fey s. j,> gheppard. . .Initial" ... .'results, here negative, but very recent work using .a mixed TTf/OA '. gelation in toluene look promising. (B) wDuco-B furniture finishes. Work don by c. J. Weis. Results negative. ,. (D.) 'Bookbinding adhesives. Work*done fey j. L. Ivans. TFT was used as a -primer for an alkali soluble, tot melt. 'Results' negative, DUP030003448 $ -- v.Web adhesion, to :wood; ..SFe*ac doue-tgr R H LaBCrg. RmviltfS rng&iiT, '/' 'l'-' ' / - ' '(E); Refrigerator. reflaiah enamel.. . lo^k- don by G. T>. I&Barre. -.. -. . . ' %. Bvthls' case* -ocbylene glycyl titanete was:applied *6 the baked- refrigerator enamel from- &..2% .and a % 'solution in hydrocarbon. After,a short flash ti8*--'the. ^fiidshKenamel; was applied".Results. were negative.... ,U; " 2*' As Agents to produce"Snsolubillgation or fast Set (A.) .' 50% solution f- 2BT in. xylene*. - applied over a. wet. film of RL-4S4 .castor oil alkydy produced .surface- ' hardness in, 1 : ..minute at room temperature*- - However* the ...film below the-, surfaceremained soft.and. the" hardened -erface showed racking"and frosting. (Work.done by j. p. sermattei}., ijeye'rfcheless, this Is. -a:- technique ` -Which might, tensed to.'produce a- fast '.setting printing" ink* sine ink films are .normally 'very'thin patent a...mil}.* A faster setting, printing ink-is wanted by such large magazine printers'&s; Curtis* Time, Xrn.* . p. Hall and others#' figments Department, intimated -.that Interchemical .were wording on this problem* using-gpon`resins " as.-, the ink vehicle and'a'titanium ester as the .'fast setting'.agent.. S.v Hochberg .is Investigating the" effectsr of mixing -'TPT'and iBf with nitrocellulose* allcyds and spans by meins-of a. 2**n^le:'spray. gun. J. \jU Euntsberger has reported that'applying tetrabubyl tlhanat over nitrocellulose film did.not produce iheolublllsaiioBi / 3 *'.. As Agents' to. Reduce Blistering of-House Paint . R.-w.-' laBerge has found that wood impregnated with is- prepoxy titanium stearate shows a.very; imrked reduction.In rat of' water absorption (30$ jplek-up In 3, months- for -the treated wbod# versus 3'cgg'pick-up' in 2 'hours for- the-untreated wood). -Isopropoxy, titanium stearate was the most effective agent for .this.- purpose of thp many candidates that were'esamlned. LaBerge.has" also found .that Ihopropoxy tltenium bleat applied, as .a"primer to.new wood reduces the blistering of #%0 Outside white significantly. . LaBerge plans- to include the titanium acylates .in his -future program on th soistare blistering problem. - . ' As, constituents' of louse paints to. -implore Durability ... , 'fiteniua stearate (39.i. and 1,2% on the- paint)* tetraete&ryl tit&nate (1 and 6,% on the paint) and tetralsopropyl titant (l.t and %f> on the paint) ifare added la the amounts sfeesm to $M) -Outside White. After 1 -year Florida exposure* the 'test. DUP030003449 ~7 - points- showed only. slight eduction in'copper screen staining and dirt collection, Tetrasteafyl. titfuaate gave tb@ best results. On-th adverse side, there. was increased yellowing and there are also eaa stability problemsV- This work ms done by B, iaserge. .'5i .As Modifiers, of Alkyd Easing Tetralmtyl fcitnat9 added In ratios ranging from 1/99 to 95/25 (solids basis) to r c -453 soya elkyd, gm a progressive Increase in yellowing and brittleness of the aliiyd film with increasing TBS content. With the normal amount of cobalt drier, 2f$ TBT in the soya aXkyd redhead the tack*free drying' time from 6 to 3 hours, but the film was soft, yellow and definitely leas flexible compared U the unmodified BO-453, 10$ under the same conditions, .ipsgbhsned the drying time slightly, in the ..absence of cobalt/' the T/alkyd films at 10/90. and 20/80 ratios (solid's basis) were- slower drying than the straight bc -453 with the normal .amount of cobalt... Ratios of TBT above lQ/90 give limited- can stability, and ratios above 2o /8g give Incompatible films. `(Above work don by H. G.. gtauffer and' j. p, gerwttei).. Additions of SB#' tocastor oil a.lkyd resulted in immediate gelation at eonhentrationg of 5^ or higher, (j* p*sermattei). Titanium, soya abylafce, added to RG-%53 soya eXRyd , showed .satisfactory compatibility at ratios of 25/75, 50/50, and 75/25 (solids basis), but the blended films were inferior to the straight alkyd in flexibility., -yellowing, hardness and .adhesion, the degree of deterioration In'these properties increasing with the titanium soya aeyXste,content. .505$ or more titanium mediate produces a marked reduction in tack-free drying time, 'but gives soft, brittle films 1 ' lesser amounts were- not .effective in reducing the drying.time of the RC-453-.aoya alkyd.. Cm stability of all blends was .good at the end of one month.- (J, f, seraattei), 6:. m Constituents of M.fiuaoB furniture sealers Tetrabwtyl titsnate was found, to/improve the. combination of drying speed, hardness., and flexibility of a px~ commit oil alky< furniture sealer, but it -.also caused bad yellowing and could pot fee used for this reason. (0. J...,Wels)," /7;' - As Agents to. Btdiac'e Wrinkling. ; . 3/%:. fBT on the. resin;.-solids,' added "to.. 93-005 Black, increases the Mrlnkllhg'film tninM&m .from.X-1/2 t 3 Mis %n the-, sun wrinkle test. This 1 cohs'idored a good lead on the wrinkling' problem with 93-005 Black.. Can. stability m& affect of .aging in the bah bn wrinkle performance are. now under study*. |j./E. Bintsherger and-Ri siuferton)i - . As pigment Bi^persing Agents isepropoxy titanium linseed acylate, isopre^^y^ titanium stearate and. isoproposy titanium soya aoy1st. were tssttfi es DUP030003450 agents to i&prove the dispersion of Monasiral Blue# but were mot found effeefcive-for' this .purpose* (\J. p, Colio), 9* As Crossliiiking Agents, for fr-p and polyvinyl Acetate This work is covered In parlim Laboratory Report #921# by D. K. Ogg, dated.. October-31 19^6$ title.* *Evaluation of fttanatltig Agents for Crosslinking of Adhesives5'. The results were negative. 10- Miscellaneous Applications . These are covered in Philadelphia .Laboratory Report #9?8* by .J, h . luntsberger# dated September 2, 19^91 titles TJ Alkyl Titamates" * " The beneficial effect of tetrabubyl titan&te `oh . Crinkling was first observed in this work by Buntsberger. - a heat resistant# aluoKLmro plgaented paint based, on tetrabutyl -titamate' as the vehicle, was developed'in. this'work, but never achieved o* mereial acceptance. The results otherwise were negative. RA88HAXX.. LAB0BATORI DUP030003451