Document Z7ZDJy5NOoKq4zoy7BdLj9kV

!0RS *, DO PONT DE NEMOURS & GO*'PANS' FABRICS & FINISHES DE3PAHTMKNT CHEMICAL DIVISION //"'A' / Ilf lit I |f9**i PAHL2N LABQRATORX CLASS A-I RESEARCH REPORT NOa PROJECT J~104? SUBJECT I AC CELERATORS FOR FURNITURE "DULUX DATE ISSUED5 April 80, 19^9 PERIOD COVERED* February 4, 19^ February 1, 19H9 PREVIOUS REPORTS ON S AME OBJECT I NONE C PREPARED W* CAa 3CHINIC APPROVED BYs RaB,, HOLMES \ N 29352 SUBJECT? ACCELERATORS FOB FURNITURE "DULUX" INTRODUCTION The "setting up os* hardening of Furniture "BULUX" is accelerated by acids* The rate and extent of setup as well as the compatibility and stability Vary with different acids. Mineral acids `-re generally not desirable because of poor eom patlbllity with the "IXJLUX" solution as well as their deteriorate ing effect on the substrate used* Several years ago a "butyl acid phosphate" was developed which accelerated the set-up ana still ms compatible^ Later an "octyl acid phosphate" was found to give a faster and more complete setup to the "BULUX" film as well as to effect a better rubbed clarity and print resistance than was previously obtained with the "butyl acid phosphate." The purpose of this work was to investigate the possi bility of preparing an accelerator which hd even better pro perties than "octyl acid phosphate*" Another purpose was to endeavor to learn the mechanism of the reaction between the "PULtJX" and the accelerator. SUMMARY Several alkyl acid phosphates have been prepared with alcohols from ethanol (Cg) to dodecanol (Gig) in place of the 2-ethylhexanol (Cg) now used. The phosphorous pentoxlde content was varied above and below that used in the current formulation,. These experimental alkyl add phosphates were evaluated as accelerators for Furniture "DUuJX"* Evaluation on walnut panels has shorn that when the same molar ratio of alcohol to phos phorous pentoxlde is used there appears to he little or no effect caused by varying the alcohols* A variance of the amount of phosphorous pentoxlde used with a given alcohol showed that as the phosphorous pentoxlde was reduced below that currently used a softer film is produced and when the amount of phos phorous Pentoxlde is increased a. hard film with slightly poorer cold crack resistance is formed* The accelerator -with the higher amount of the pentoxlde appears to have somewhat poorer stability* It is concluded that the present octyl acid phos phate accelerator formulation (C1?M-) gives the optimum cure from the standpoint of rubbed clarity and cold crack resistance and has about the best composition for stability., PATENT SITUATION Octyl acid phosphate is covered by U*S* Patent 2, B7K HU7 assigned to the Beiohhold Chemical Company* The duPont Company has been granted a free license for the preparation ana use of this compositioiSo The work carried out under this pro ject has produced nothing patentable in light of previous patents in the field* DUP030001153  ~3 3&CFERXMSNFAL The rate of cure os? hardening of ureaformaldehyde resins, such as those used in Furniture MDinux" can he great ly accelerated by the addition of an acid. Because of the several disadvantages of mineral acids, suoh as incompatibility and corrosion, a butyl acid phosphate composition was used for some time, U.S. R^tent 2,274,447 {Reichhold) disclosed an oetyl acid phosphate composition which was also found to accelerate this cure rate, Evaluation studies showed the latter material to give a more rapid cure, and a better all-around finish, Previous worfc here was directed only toward the development of the pro cess for the preparation of the octyl acid phosphate. The work under this project has been directed at investigating other albyl acid phosphates in the search for a better accelerator than the one now in use and to endeavor to learn something of the mechanism of the reaction involved* The complex nature of the product limited the analysis to the determination of acid number, non-volatile content and color. The acid number was determined by titrating a weighed sample of the material in neutral alcohol with, standard aqueous sodium hydroxide solution. All of the solids determinations in this report were determined by placing a weighed sample of the material in a. shallow glass dish, in an air circulating oven at 1050 o for&ur hours and'noting loss in weight* (More recent work, at the Oldbury Eleotro-Chetnical Company laboratory indicate that a non-circulating oven gives more consistent results). All color comparisons were made with the Berlin scale. The early work on the preparation of ootyl acid phosphate indicated that if the temperature of the reaction was allowed to rise very much above 4oC, the product t o old separate into two layers. Therefore in thi$ writ cooling baths were provided at all times to prevent the tempertore of this exo thermic reaction from rising too high. In the course of the present wortc several alcohols have bean investigated in place of the 2ethylhexanol la the present octyl acid phosphate formulation (C-l?14-).. This CL.3.74 formulation also contains a small amount of ethyl Cellosolve and rubutsnoln The various alcohols were used to replace the 2-ethylhexanol on ah equal mole basis, so that the weight of alcohol varied- considerably from the lowest to the highest molecular weight alcohol used, However, it was felt -feat this would give a fairer comparison of the alcohols since the function ality was always the same, \ The amount of non-volatile material after the re action varies somewhat from batch to batch and also with the molecular weight of the alcohol, so that all of the accelerators were diluted t 50# non-volatile material with toluene. Repre sentative runs with different alcohols are tabulated in Table t9 DUP030001154 It Is readily seen that as the molecular "eight of the alcohol increases, the acid number of the accelerator at 50# solids decreases. The last item in this table {n-butyldihydrcgm phos phate) ms included for academic reasons as a material whose exact composition is known. The sample designated 2216-133 is a. laboratory batch of standard G-lJk accelerator. The amount of phosphorus pehtoxide used wi th 9. given alcohol tms also varied to learn the minimum amount which wouia give satisfactory cure. The phosphorus pentoxlde was also in creased In order to discover the maximum amount that could be incorporated into the formulation and to determine whether the cure time could be shortened or the bake temperature lowered. Table II shows the composition of the accelerator when the amount of phosphorus pentoxlde was varied while keeping the pr*t o'-* n-octanol constant. No more than.150 g0 of j ?205 could be in corporated into the reaction mixtures. A typical laboratory experiment {2216-163) will be described. To a 1 liter, three neck flask equipped with an anchor stirrer and a thermometer Is added loo g. of toluene, 9 g. of (ethyl) Cellosolve,and 100 g. of n-ocatanol. To this Is added lno g, of phosphorous pentoxlde in small portions over the. period pf about two hours. A stopper is kept in th unused neck of the flask except at such times as additions are made. As the reaction is extremely exothermic an ice bath is raised around the flask fiom time to time in order to keep the temperature below 350* It has been found that the ?25 Is beat weighed oulckly and ,then stored in a desiccator over P2O5 between addition. After all of the PgOc has been added the mixture is stirred for one hour and then 16 g. of rubutanol is >dded slowly. The final mixture is allowed to stir for an additional hour before being sampled for analysis. If the non-volatile content was found to be over 50# sufficient toluene was added with stirring to bring it down to 50# tt 0 VALUATION The ootyl acid phosphate accelerator is used by add ing 5# solid accelerator to the Furniture 'OULUX" based on the solid ureaforataldehyde resin in the This amounts to 2 parts of the accelerator solution to 96 parts of "DULUX" {RK-5`760). Therefore all evaluations were carried out with these amounts. It was found to be very difficult to pick up small differences in performance of the various accelerators when pours of the HK-.5760 accelerator solutions we^e baked on glass panels. Therefore sauries of accelerators which were considered as representative of the point being considered were evaluated following the standard procedure on walnut veneer panels. The panels are treated as followss Ca) sanded, (b) was coated tilth 19360 Sealer, scuffed, (c) filled with 27-5017, air-dried overnight Cd) sealed with 19360, dried <e) a 2 mil topcoat applied - one half of the panel being sprayed with the h k ~576o - C-174 control and the other half with KSC5760 plus the experimental accelerator. The panels are then air-dried for one hour and finally baked for two hours at 120F. At the DUP030001155 1 ~iu same time pours of the topcoats are made on glass and the time for the Him to become tack free is noted. After the films, have been baked* the panels are allowed to oool and are then processed by sanding and buffing, The panels are rated on their rubbed clarity* l,e, freedom of base and degree of polish, and on print resistance,; This latter test Is made by applying 2 ana -4 pounds per souare inch to piece of duok cloth placed on the film overnight. The amount of printing of the weave of doth on the finish is compared to the standard. The results obtained with the accelerctor evaluated are given in Table XXI, 'From this table it can be seen that When the standard amount- of P^c is used there is very little difference in effectiveness of the accelerator although the alcohol is changed from 04 to Cl2 The rubbed clarity of panels 1noroases as the amount of P2O5 used with a given alcohol Is increased while the cold crack resistance falls off. This is to be expected since a harder film dll take a better polish but it is more brittle and hence has poorer cold eraok resistance. It is also seen that n-butyldihydrogen phosphate and phosphoric acid will, our the film although not as well as the alkyl acid phosphate ac celerators,, . Xt Jtias been shown that the addition of 2 to 4$ of water to the B&-57bo accelerator solution dll cause it to gel in from 1 to 7 days at elevated temperaturesfl e,g, 120F o However, film prepared from these solutions containing additional water before they have set up do not show any improved or degenerated properties, Trlalky! and triaryl phosphates will not cure the RK-.5760 on baking. HOPS or ACTION The method of action of these alkyl acid phosphate accelerators is not understood. Because of the complexity of the two solutions involved it is felt that a study of the reaction is beyond the scope of this work. However* it is now thought that the role of the acid number of the accelerator Is minor. Table X shows the acid numbers cf the alkyl acid phosphate accelerators varying from 159 to 2^0 and yet apparently there was little difference in the effectiveness of any of them. And while the n~butyldihydrogen phosphate with' an acid number of flS cures the film* it is not as good as the alkyl acid phosphates. Further work along this line is not contemplated at this time. DUP030001156 d dmtt> to a 3 i> o J4a 3 oto * 8 3 c!B o o 1 03 d 8 iCQ K\ US 9- R 50 4 4 NS H 1*2. US 4 o US 4 Qus o0 uHs a H Ho 3 t* ON US NS o Ss O R US CM n s dCD 1Q p 3 4*' d ^* <O *9 8 d1 H 3 ft & ffi J? cm tWS CV1 H HH i$s CQ OS vo n s us 4 > O d & or4 d Ho 33 CM V) vVoO vot**- Ovo On - Ci*M~ NS H OP S PS Q 3 O ISO VO CSV H 4 OS VO 18P d r! NS CM OS H O US H CM CM H W CM H r*. *O3i 8 P Iffi t 8 3 *3 8 8 St oPCJ s O a0 o d Q8 HO >*4 13 ft CQ c CJl 8 CM csl | csfito o H US CM o NS R NS NS NS VO d CJ VO o o <S5ri H I VO (0 H CM rl rl H J> sA vi> HI H H CM CM CM H H H CM V& v& V^ H H HI r-5 CM CM CM CM CM CM CM CM CM CM CM CM , ' \ DUP030001157 mni Depiffnatlon 223.6-193 2216-194 2216-169 2216-172 2216-163 ,,>e *2i 20 .35 50 75 loo 2216-186 2216-173 2216*190 100 125 150 Acid Uo0 76 135 X?4 212 211 200 235 233 % Solids Remarks SM 42,8 55?0 69,6 70,4 Tbie represents the Std, amount of RgOg 72,8 Only tt-ootanol used 73 0# 75 7 Stable for only a short time DUP030001158 TABLE III Accelerator Designation Alcohol Used Parts of Overnight ajt Bobbed Printing p2<?6 Clarity ... Crack C-174 2-Ethyl- 100 ... hexanolf 6 98 2216-2042216-130 2216-193 n-Butanol " 'f n-Butanol n~Octan1ol 50 100 20 5 7- 54* $+ 7+ A 5 54- 2216-16$ n-Oetanol 50 6 6 2216-163 n-Octanol 100 6 9* ^ 6 2216-173 2216-190 2216-211 nOctanol 125 n-Ootanol 150 ' n-Dodecanol 5 99 9 645 6* 4*S* 2216-162 2216-212 2216-200 n-Bodeoanol 100 nDodecanol I50 n- Butyl clihydrogen phosphate Phosphoric acid ^ 051 6 9 7* 7* 6 7 7 74- 6 76 Cold 6- ' 6 94* 6 Crr 64* 6 7* ' (a) 100 parte FgC^is standard (to) 3*15% based on U-F DUP030001159 Djstrlhutlom Mr, John Marshall# "Wilmington Mr,, JoB Bullitt# J* Philadelphia Dr, R,B0 Davis# Flint Mr,, AoF, Schlldhauer# Fairfield Mr, RoEa Thomas# Newburgh Mr, H0Ej, Lackey# Wilin. Mr, H,L0 Prlddy# Parlin Mr, A,,Ko Burke# Wilmington Dr, L0Go Wise, ExpoStation# Wllm, Report No,, 95^ DUP030001160