Document DMdd5wL05mvooYj0212NNDy3d

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IgfBOPPQfXOH ^<ff^iy<vVw>sg^giwwawMBMOTwM<iCTW<^*iwmwcwg!iwwa^^ The primary purpose of this rs.search projsot . was to, develop a polymerised ureaformaldohyd for use as an inexpensive non-settling flatting agent satisfactory for use in lacquers,, varnishes and synthetic resin compositions0 'this work was covered by major experimental project J-3X1C. dated November kc l$4l0 The polymerised ureaformaldehyde resin in question has also been evaluated as a dehydrating agents decolorizing agent0 gas adsorb, lag materialsanding aid and' ion exchange .resinTM The regent decision on the part of the management to place long range research work In the background due t urgent war problems has made it necessary temporarily to terminate the work on this research projecta gome.of the phases of this problem have been complete&p .some were, being actively worked onP and some had not yet been considered* The intent of this re port is to place m record the present -status of this problem so that future investigators may proceed with this work when time permit So mmmt j j t o o g w u j s x o k b The polymerized resins evaluated in this work were prepared by treating heated solutions of ureaformaldehyd resin with .small amounts of .mineral acid accelerator* Sulphuric and hydrochloric, acids were found to be the most effective accelerators0 and temperatures just below the boiling point of the carrier solvent were generally employed to carry out the polyme.rizatio.no When examined as-flatting agents .these gells were used in mill bases without removing the .carrier solvents but when evaluated in other capacities^ this solvent was driven . off with heato gelled ureaformaldehyde resin , has been found of interest as a flatting agent for J3PULUX|{> .Buco% and enamels Improvements in.settling properties and flatting strength will be required before commercial consideration is given to this type of product,, but further effort could undoubtedly overcome these ..minor objections* Although, dry gelled mreaformaldehyda appears to be an effective gas adsorbing materials we have found it to be impractical for this us as it does not completely remove toxic gases from airp and we know of -no method of recovering the resin after such use.o Icon!ally it could probably not ooapete with activated carbon* - (om) DU P030001062 e2 (Jelled ureaformaldehyde has "been found ineffective as a dehydrating agent,, decolorizing agent , sanding aide* and as an Ion exchange resin for water purification., EXPERIMENTAL The thought behind the preparation of the material with which we are dealing was to polymerize a ureaformaldehyde resin aolution with the object of obtaining a gell structure of the same general type as silica gel,, (a dehydrating agent) and Santooel (a flatting agent)0 Both of these materials are silica type hydrogels and are produced by the Davison Chemioal Company and the Monsanto Chemioal Company respectively,, Al though it is possible to polymerize a solution of ureaformalde hyde resin by heat alone* this was found impraotioal due to the time involved* and as a result* most of our-work was carried out on the basis of a gelled resin which had been polymerized by means of both accelerator and heat0 The various phases of our work are dealt with below,, 10 Celled ureaformaldehyde resin has been found to be an interesting flatting agent for both "DULUX" furniture finishes and laoquers0 However* time did not permit the pro duction of a flatting agent whioh could be considered entire ly satisfactory in all respeot80' In the oase of HDULUXH furniture finishes* the ohief draw-baok was the fact that when satisfactory flatting strength was prooured* poor settling results were obtained* whereas when satisfactory non-settling was developed* the flatting strength of the finished material was deficient when compared with Santooel0 In the oase of pyroxylin finishes* a grinding cycle In exoess of that em~ polyed with stearate mill bases was found to be neoessary* and inferior settling properties in comparison with stearate was experienoedo The flatting strength was entirely satisfactory In the oase of pyroxylin produots0 The Philadelphia Laboratory has examined various gelled ureaformaldehyde resins as flatting agents for varnish and enamels They have reported them unsatisfactory for use in varnish as a oonsequenoe of the high butyl alcohol content* and satisfactory in enamels* with the exception of the high aoldlty* and in some oases poor flatting strength. It is obvious that all of the objections indicated above oould probably be overcome by a oontinuatlon of this work 2,-, Both water soluble and organic solvent soluble ureaformaldehydeswere found to be unsatisfaotory as a dehydratIRS agent.. DUP030001063 ' ' -3 ' 3o G-elled ureaformaldehyde resin was found to be an Interesting gas adsorbent when evaluated with olorine gas,, and air saturated with hydrocarbon vapor0 The results of this work were oovered in Parlin Laboratory.memorandum report No0 3 of January 194-20 On the basis of our findings*, samples of this resin were submitted to representatives of the Chemical Warfare Servioe for consideration as a gas adsorbent for gas masks,, They reported the material unsatisfactory for this purpose as it did not completely remove toxic gases from air Although gelled ureaformaldehyde appears to be a gas adsorbent, we do not anticipate any practical application of this property 4-a O-elled ureaformaldehyde resin wae found to be un satisfactory as a decolorizing agent0 5o Q-elled ureaformaldehyde resin was found to be un satisfactory as a sanding aide In laoquer sealersc 6o Reoently published work by the Resinous Products and Chemical Company on completely polymerized phenolic resins for use as Ion exchange resins for water purification problems, led us to evaluate gelled ureaformaldehyde in this capacity It was found to be completely ineffective In removing either anions or oatlons from low concentration solutions of dissolved salt 7c Our work indicated that straight heat gelled urea formaldehyde resins were not praotloal as the gelation time was too long (a matter of days) and the resultant polymerized resin was not rigid enough for satisfactory grinding,. As a result of this initial discovery* all subsequent resins evaluated were prepared by the use of a mineral aoid aooelerator and heat,, It is not entirely essential that heat be used but it greatly hastens gelationo It was found that the gelation of high concentra tion solutions of ureaformaldehyde resins (4o~>60# solids) pro duced gels which were so dense that poor grinding and subse quent unsatisfactory settling was experienoed0 Our most success ful resiilta were obtained In the range of 10-25# solids prior to gelation,. Of the group of mineral aoids evaluated,, sulphuric aoid and hydrochloric aoid appear to be the best accelerators for our purpose,, In the case of sulphuric aoid a soft easy grinding resin of good non-settling properties was procured,, but poor flatting was experienced,, In the oaee of hydro> chloric aoid0 a highly rigid gel was formed which resulted in difficult grinding with subsequent bad settling,, Definitely superior flatting results were obtained In the oaee of hydro chloric aoid than in the oaee os sulphurlo. (OVER) DUP030001064 o4o 9,, In our Initial work no attempts were made to neutralize or remove the aoid catalyst used In preparing the gelf and no appreciable detrimental effect was noted in the film quality of the finished produota However^ oanoorrosion was experlenoed with this procedure,, In our later work ammonium hydroxide was used to neutralize the aoid catalyst and satis factory results were obtained by thie methods 10o Water soluble ureaformaldehyde end phenolic resin gels were evaluated as flatting agents and found to be unsuit able o In the case of ureaformaldehyde resinsp an extremely dense gel was obtained whioh could not be satisfactorily ground^, whereas the phenolic resins produoed a soft gummy precipitate of unsatisfactory color,, In evaluating gelled ureaformaldehyde resins as flat ting agents in MDULUX" furniture finish,, both the RF-5718 and RF-5728 formulas were used,, RF-571S is a product which contains carnauba wax as flatting agent and RF-5728 contains 3antooel0 The RF-5718 formula has a soluble oontent break-down as follows? RC-721 solids a-302 G-652 RL-255 (solid) H4 0-694 17015^ 80O5 lo25 II0I5 4,,30 6a 2^ The RF-5728 formula has a break-down composition as follows? RC-721 solids G-302 6-652 RL-255 (solid) H~4 (solid) G-620 I60 7 066 1 n 10 12.56 A0 A In our work gelled ureaformaldehyde resin was sub stituted for 0-694 in the oase of the RF-5718 formula and for (M>20 in the oase of the RF-572S formula and oompared directly with the standard materials containing carnauba wax and Santooel respectlvely<, All the conclusions based on "DULIIX" furniture finish were made on this basis,, DUP030001065 -'5- In the case of lacquer evaluation the 1661* Type II "Duoo" formula was used* A solids breakdown of this material follows8 PX g -356 G~, 60S H-1I6 H-22 0-217 9 c, 8$ 6,-2 2*2 3*2 1-3 Gelled ureaformaldehyde was substituted dlreotly for the G-217 in this formula for direct comparison with the stand ard met erial 0 In all cases the gelled ureaformaldehyde was made into a suitable mill base by grinding in a laboratory mill,, It was found that satisfactory grinding oould not be obtained in a one quart mill in a reasonable length of time, this fact being previously noted In the case of Santooel mill baseflo Therefore,, one gallon orooks were used* using a ratio of 2 parts of pebbles to one part of charge* the usual grinding oyole being 48 hours* In examining gelled ureaformaldehyde as a dehydrat ing agent,, the gel was carefully dried in a 100*0* oven for three days prior to evaluation* The evaluation was made by passing water saturated air at room temperature through a weighed sample of the dry gel for varying periods of time and establishing a curve* In no oase was the resin found to adsorb more than 10$ of water vapor from saturated air and it is obvious that its effioienoy is not great enough to warrant further consideration In evaluating gas adsorption* pure ohlorine In one oase and air saturated with hydrocarbon vapor in another oase was passed through a sample of dry gel* and the inoreaae in weight notedo It was found that as high as 48$ of ohlorine oould be adsorbed by a gel prepared from a 3$ solution of ureaformaldehyde resin* whereas as high as 28$ hydrocarbon vapor could be adsorbed by this same type of gel This work is more completely covered in Parlin Laboratory memorandum report No 8 of January 8* 194-2* under the subject of Gelled Ureaformaldehyde Reain as a Gas Adsorbent,, In examining dried ureaformaldehyde resin gel aa a decolorizing agent, Impure dlbutyl phthalate was employed and Daroo was used as a, oontrol When treated by the standard (OVER) DUP030001066 4 testing method which consisted of adding 2$ of the decolor izing agent to the impure dibutyl phthalate and heating in an oven at 70*0 for one half hour, it was found that the Daroo gave satisfactory decolorizing aotion whereas none of the gelled ureaformaldehyde resins did. In examining gelled ureaformaldehyde as a sanding aide; a mill base of this material was prepared and the product was used as a replacement for zinc stearate in 19 >5 p a 21$ solids Type I patent sealer<> It was found that gelled ureaformaldehyde was very poor in this capacity,, In evaluating resins of this type as ion exchange resins, 10$ of the dry gelled resin was added to a one half percent sodium chloride solution using an equal amount of resin with distilled water as a oontrol. After allowing these materials to stand overnight the pH was determined on the treated and untreated water.' It was found that treat ment with gelled ureaformaldehyde resin tended to make the solution more aoidiCp but as this increased aoldity was also in evidence with distilled water,, it was concluded that the gelled ureaformaldehyde is not effective as an ion exchange resin and that the acidity produoed was in all probability due to the residual acid aooelerator in the resin. EFOaMON \ i DUP030001067