Document Ve5aJ89O6O7xgXmzr2L0qVDg

Indexed C. W. Theobald, Wilra. F&F ) In J. A. Klacsmann, Wllm. F&F) Turn W. P. D. D. B. Lawson, Cochran, W1!ilm. McBurney, It P&11 F ii \1 ' In Turn J. W. Nestor, R. B. Davis, C. F. Kalb, n n ti 1! 1 II n ^i) In Turn J. C. Richards, Newburgh 0. H. Bullitt, Jr., Exp. Sta; . L. G. Wise, Exp. Station G. I. Mulholland, Flint File: I865 E. I. DU PONT de NEMOURS & COMPANY F&F RESEARCH DIVISION MARSHALL LABORATORY RESEARCH REPORT WATER SOLUBLE POLYMERS AS PRIMARY BINDERS FOR FINISHES - II Date Issued: Period Covered: Project No. Previous Reports Notebook Nos*. 1/3/62 Feb. 1, 1961 to Sept. 12, 1961 P-1502 R-61-19 7362, 7545 AGA:CKI:pas 1/5/62 PREPARED BY: Qj MA. G. ARMOUR APPROVED BY: C. K. IKEDA / Indexed C. W. Theobald, Wllm. F&F ) In J. A. Klacsroann, Wllm. P&P) Turn W. P. D. D. Lawson, B. Cochran, McBurney, Wnilm. IT P&n P II ]K) 1 In Turn J. W. Nestor, R. B. Davis, C. P. Kalb, IT ff II If II II 1\i>) In Turn J. C. Richards , Newburgh 0. H. Bullitt, Jr., Exp. Sta; ' L. G. Wise, Exp. Station G. I. Mulholland, Flint Pile: 1865 r -62-1 `wnFXED'' E. I. DU PONT de NEMOURS & COMPANY P&P RESEARCH DIVISION MARSHALL LABORATORY ___________RESEARCH REPORT WATER SOLUBLE POLYMERS AS PRIMARY BINDERS FOR FINISHES - II Date Issued: Period Covered: Project No. Previous Reports Notebook Nos: 1/3/62 Feb. 1, 196I to Sept. 12, 1961 P-1502 ' R-61-19 7362, 7545 AGA:CKI:pas 1/5/62 PREPARED BY: T." n. ARMC APPROVED BY: 4:' DUP030009257 TABLE OP CONTENTS Page Number INTRODUCTION OBJECTIVES SUMMARY AND CONCLUSIONS ACTION TO BE TAKEN PATENT SITUATION ACKNOWLEDGEMENTS DISCUSSION 1 1 I 3 l 5 k. Preparation of Itaconic Acid Copolymers 5 1. By Bead Polymerization 2. By Solution Polymerization 5 8 B. Properties of HMDA Crosslinked IA Copolymer Films 10 1. Effect of Copolymer Composition a. Itaconic Acid Content b. Degree of Crosslinking 2. Pop Bottle Polymers Versus Flask Polymers 3. Effect of Casting Solvent on Film Proper ties 4. High Styrene Copolymers Crosslinked with Long Chain Diamines 10 12 12 14 16 16 C. IA Copolymer/HMDA Sheet Metal Primer 16 1. Formulation 2. Properties a. Flexibility, Hardness and Adhesion b. Salt Spray Resistance c. Blister Resistance d. Cost D. Comparison of IA Copolymer/HMDA System with Commercially Available Water Soluble Systems EXPERIMENTAL Bead Polymerization of MMA/BA/IA Solution Polymerization of S/EA/IA Solution Polymerization of MMA/BA/IA Sollds/Vlscosity Relationship Experimental Automotive Sheet Metal Primer-W-27494 Experimental Automotive Sheet Metal Primer-W-27501 REFERENCES 16 18 18 19 19 20 21 23 23 24 25 25 28 28 30 DUP030009258 ABSTRACT Water dilutable itaconic acid terpolymers are under evaluation as primary film formers. Use of diamines as crosslinking agents provide hard, flexible and adherent coatings. Efforts to develop a practical bead polymerization process for these terpolymers were unsuccessful. A solution polymerization process using refluxing isopropanol was developed and is currently employed. The use of these copolymers as a binder for an auto motive sheet metal primer was investigated and is covered by this report. DUP030009259 MMA BA EA IA S 2-EHA HMDA ABBREVIATIONS Methyl Methacrylate - Butyl Acrylate - Ethyl Acrylate - Itaconic Acid; - Styrene - 2-Ethylhexyl Acrylate - Hexame thylenedlamine DUP030009260 WATER SOLUBLE POLYMERS AS PRIMARY BINDERS FOR FINISHES - XI INTRODUCTION: Recent interest in water borne finishes for industrial applications has been stimulated by their reduced air contamina tion, fire hazard and solvent cost. Successful development of new water based coatings would provide F&F with increased sales and profits in this growing market. J. C. Fang (Ref. l) established that copolymers containing 10$ itaconic acid are water dilutable when converted to their ammonium salts and provide attractive coatings when crosslinked with diamines. This report covers the preparation and evaluation of itaconic acid copolymers as the binder for a sealerless-.primer for automotive "Lucite"*. Evaluation of the copolymers as adjuvants for emulsion latices is under Investi gation by E. R. Werner, Jr. and will be reported separately, OBJECTIVES: The broad objective of this project is to determine the usefulness of water soluble polymers as binders for finishes. Specific objectives of the work covered by this report are (1) develop a laboratory process for the preparation of water dilutable itaconic acid copolymers suitable for laboratory scaleup (2) evaluate the copolymers as binders for a sealerless sheet metal primer to be used under "Lucite''* and (3) develop basic Information on commercially available water soluble coating vehicles. SUMMARY AND CONCLUSION: Bead polymerization was examined as a method of preparing itaconic acid copolymers. Although bead polymers containing as much as 9% combined itaconic acid were obtained, none were soluble In aqueous ammonia. In fact these polymers precipitated from butyl cellosolve upon addition of 40 volume percent of aqueous ammonia. As a result attention was returned to solution polymerizations, the method originally used by Fang (1). A brief study established that substantially anhydrous conditions must prevail during polymeri zation to achieve water dilutable polymers. With this knowledge a reproducible, high yield procedure for preparing copolymers on a 12li ter scale was developed. Selected copolymers prepared by this method were shown to be essentially equivalent to Fang's copolymers by relative viscosity and film property determinations. * Registered Du Pont Trademark DUP030009261 2 The solubility of itaconic acid copolymers in aqueous ammonia vary considerably and are highly dependent on their composition. Those containing 40-70$ styrene require as much as 20$ butyl cellosolve to achieve clear solutions. Of the copoly mers examined to date, only the acrylate/itaconic acid compositions were soluble in aqueous ammonia alone. All others required mixtures of aqueous ammonia and an organic solvent. The film properties of several hexamethylene diamine crosslinked Itaconic acid copolymer compositions were determined as clears over Bonder! te panels. -..The''' following ^information `was . obtained ffom the study. 1. Ten percent itaconic acid gave optimum balance in aqueous ammonia solubility and film properties. Polymers with 5$ acid not only had poor solubility but did not cross' link sufficiently to yield solvent resistant films. Poly mers with 15$ acid, although quite soluble, gave films with an inclination towards brittleness. 2. At least 75% the theoretical amount of hexa methylene diamine is required to achieve optimum solvent resistance. Additional amounts beyond this seem to have little effect. 3. Films cast from organic solvents are equivalent in properties to those cast from solvent mixtures containing at least 80% water. 4. Copolymers containing 70$ styrene are very brittle when crosslinked with hexamethylene diamine. Replacement of some or all of the latter diamine with a long chain diamine gives improved flexibility but only with a simultaneous sacrifice In hardness and solvent resistance. Black automotive dip primers were formulated from selected styrene/acrylate/itaconic acid copolymers modified with hexamethy lene diamine and evaluated against 64-1690. Salt spray resistance of the primers was superior to 64-1690. "Incite" and "Dulux 100"* automotive topcoats had excellent Initial adhesion to the primers. On exposure in the humidity cabinet "Incite" lost adhesion and blistered. "Dulux 100" did not change. Calculations using mini mum monomer costs indicate that the experimental primers will be twice as expensive as 64-1690. A portion of their high cost re sults from the use of a solvent mixture containing butyl cellosolve. * Registered Du Pont Trademark DUP030009262 -3- A literature survey of competitive water soluble coating vehicles was made and the following baking systems selected for laboratory examination. SMA 1000A Carboset 531 Melaqua 600 Cargill 750 Arolon 304 Arolon 1001 Gantrez AN Resydrol P-411 Epok A-1700 Resin C-50 Aqualon 200 The first six were evaluated as clears; only Melaqua 600 and Carboset 531 gave noteworthy films. These were examined further as sheet metal primers for "Lucite" and "Dulux 100" and found in ferior to HMDA crosslinked IA copolymers. ACTION TO BE TAKEN: Further work under the broad project objective, namely, to determine the utility of water soluble polymers as binders for finishes, will include (1) evaluation of water soluble itaconic acid terpolymers as binders for appliance and automotive topcoats (2) a limited program to establish possible utility of the terpolymers as binders for an automotive body primer and (3) continued develop ment of basic information on commercially available water soluble coating vehicles. Additional laboratory work on the process for preparing the terpolymers will be conducted only if a decision is made to obtain patent coverage. The high cost of the sealerless "Lucite" automotive primer and the susceptibility of the primer/,,Lucite'' coating combination to humidity cabinet blistering make it unattractive, therefore no follow-up work is proposed. PATENT SITUATION: Report R-62-5 by E. R. Werner, Jr. covers all patent activity related to this project. DUP030009263 -4ACKNOWLEDGEMENTS: The author wishes to thank C. J. Holliday for his diligence in performing the laboratory work covered in this report. Thanks are also due to E R Werner, Jr., J. C. Pang, M. Greif, R, W. La Berge and W. M. Duffy for their assistance through many helpful dis cussions during the course of this investigation.. DUP030009264 -5- DISCUSSION; A. Preparation of Itaconic Acid Copolymers Previous work on this project by J. C. Fang established that acrylic terpolymers containing 5-10$ of itaconic acid give water dilutable ammonium salts upon treatment with aqueous ammonia. Films of these polymeric salts convert on heating to water insoluble, alkali and organic solvent sensitive coatings. Fang showed that addition of diamines to the solutions prior to baking greatly im proved the resistance properties of the films. Thus, mixtures of S/EA/IA copolymer and hexamethylenediamine were shown by him to give hard, solvent resistant, flexible and adherent coatings. These properties suggested that they would be useful as binders for water borne topcoats and primers. Previous polymer preparations were generally carried out in pop bottles. A method was needed for preparing polymers on a much larger scale to provide the material necessary for evaluation and a more realistic basis for estimating polymer costs. Bead polymerization was examined initially because it was expected to . offer advantages in (1) operability in existing equipment (2) ver satility and (3) cost. I -By Bead Polymerization In bead or suspension polymerizations a monomer or mix ture of monomers is dispersed by rapid agitation Into droplets suspended in a second liquid phase in Which both monomers and poly mers are essentially insoluble. The monomer droplets, which are larger than those in a true emulsion, are then polymerized while dispersion is maintained by continuous agitation. Agents are added to the suspending liquid, which is almost always water, to prevent coalescence of monomer droplets during polymerization. Polymeriza tion initiators or catalysts soluble in the monomer phase are used. Depending on the monomers, hard or soft spheres, beads, pearls or irregular shaped particles are formed making separation from the aqueous phase easy when stirring is discontinued. Although sus pension polymerization has become important commercially, relatively few publications have appeared and its scientific aspects have re ceived very little attention. The reasons for Its industrial development are clear and include rapid dissipation of heat of polymerization and formation of granular, easily filtered products whibh can be obtained directly from many polymers otherwise difficult to break up from hard, tough, adhesive or rubbery masses. The necessity for coagulation of latex and extensive washings of emulsion polymers are avoided. DUP030009265 -6- This process was also chosen for the preparation of itaconic acid copolymers because it offered the advantage of complete solvent ehoice. That is, the bead obtained could be dissolved in aqueous ammonia or any other solvents for the polymer. Bead polymers were successfully obtained when methyl methacrylate, butyl acrylate and itaconic acid were copolymerized in water as the suspending liquid. Triton X-100 was found to be the most effective suspending agent although others such as poly vinyl alcohol could be used. When a 50/40/10 ratio of MMA/BA/IA was charged to the reaction vessel* suspended with one and one half its weight of water and polymerized, the resultant bead polymer contained only about 1% itaconic acid. To obtain a bead polymer containing 10% itaconic acid (determined by acid number) a 50/40/30 charge ratio was required. The bead polymers, obtained in 70-85% yields, were swollen, but not dissolved by aqueous ammonia. They dissolved in butyl cellosolve but precipitated upon conversion to their ammonium salts by addition of aqueous ammonia. All attempts in cluding use of 1) higher itaconic acid charge ratios, 2) dodecylmercaptan to reduce molecular weight, 3) acids and/or salts to increase IA concentration in the oil phase and, 4) co-solvents such as isopropyl alcohol, failed to produce a bead polymer soluble in aqueous ammonia. Bead polymerizations of styrene with ethyl acrylate and itaconic acid were generally unsuccessful. The slow polymeri zation of styrene with itaconic acid made it difficult to keep the beads dispersed for the duration of the polymerization. When successful, the beads were usually so soft that coagulation took place on standing. These polymers were also insoluble in aqueous ammonia. No bead polymers of acrylontrile, butyl acrylate'and ttaeonlc'acld were obtained because of coagulation during polymerization. Addition of water to organic solvent copolymerizations of itaconic acid was explored to determine its effect on polymer solubility in aqueous ammonia. It was hoped that a logical expla nation for the insolubility of the bead polymers in aqueous ammonia could be found. Two hundred grams of a 50/40/10 MMA/BA/IA polymer were prepared in 250 g. of butyl cellosolve containing 50 g. of water. Addition of 10 cc of 5% aqueous ammonia to 15 cc of polymer solution caused the polymer to precipitate from solution. Poly merization of the same monomers in anhydrous butyl cellosolve under identical conditions gave a polymer which, when treated with the ; same amount of aqueous ammonia, gave a clear, homogeneous ablution. This decided difference in water solubility shows that water has a definite effect on the polymerization of itaconic acid. Table I lists some of the polymers prepared in the presence of water. DUP030009266 -7- TABLE I SOLUTION POLYMERIZATION OF ITACONIC ACID IN PRESENCE OP WATER Code W-27441 W-27445 W-27448 W-27450 W-27451 W-27456 Polymer Composition Solvent Composition MMA/BA/IA 50/40/10 50 g. HpO; 250 g. Butyl Cellosolve MMA/BA/IA 50/40/10 50 g. H20; 250 g. Butyl Cellosolve MMA/BA/IA 50/40/10 25 g. H20; 275 g. Butyl Cellosolve MMA/BA/IA 50/40/10 5.5 g. H20; 300 g. Butyl Cellosolve S/EA/IA 40/50/10 20 g. HoO; 200 g. Isopropyl Alcohol MMA/BA/IA 55/40/5 25 g- HgO; 175 g. Butyl Cellosolve N.B. 7362 Page 66 70 73 75 76 82 All of these polymers except W-27450 showed a similar decreased water solubility. Polymer W-27450 was prepared in the presence of 5.5 g. of waterj that is, one molecule of water per carboxyl group of Itaconic acid in the hope of observing decreased solubility at that level of water. This polymer possessed normal water solubility. The exact amount of water necessary to produce decreased solubility was not determined. Water is believed to produce this effect by changing the reactivity of itaconic acid; possibly through ionization or formation of a complex. Conductivity measurements of itaconic acid in butyl cellosolve and isopropyl alcohol when titrated with water, gave curves which were completely normal and did not show any un usual effects. DUP030009267 -8II By Solution Polymerization: Solution copolymerizations of itaconic acid require a solvent that is (1) inexpensive, (2) readily removable, (3) miscible with water and (4) a solvent for the polymer formed. Initial solution polymerizations of itaconic acid were run in butyl cellosolve. While this solvent is water soluble, it is expensive ('$..23/lb.) and has a high boiling point, 145C., making it difficult to remove. Isopropyl alcohol, however, possesses the above requirements. Soluble polymers are obtained when acrylic copolymers of IA are prepared in refluxing iso propanol. Its boiling point, 88C., is a convenient temperature for polymerizations, providing polymers with reproducible mole cular weights. Furthermore, itaconic acid, which is not soluble in many organic solvents, is very soluble in isopropyl alcohol, permitting homogeneous polymerization conditions. Polymerizations on a scale-up to 12 liters were achieved in anhydrous refluxing isopropanol without incident suggesting that scale-up to even larger size batches will be a relatively simple matter. Table II lists some of the polymers prepared in refluxing anhydrous Isopropyl alcohol. DUP030009268 - 9TABLE II ITACONIC ACID COPOLYMERS PREPARED IN REFLUXING ISOPROPANOL Code w-27438 W-27440 W-27455 w-27463 w-27465 w-27466 W-27467 W-27468 W-27469 W-27479 W-27484 W-27485 W-27486 W-27487 W-27488 w-27489 W-27490 w-27492 w-27495 w-27496 w-27497 w-27498 w-27499 W-27502 w-27503 w-27504 w-27505 Reaction Con- Relative N.B.7362 Polymer-Composition Time (Hrs.)version Viscosity Page S/EA/IA - 40/50/10 S/EA/IA - 40/50/10 5.5 16.0 MMA/BA/IA - 55/40/5 3.0 MMA/BA/IA - 50/40/10 3.0 MMA/BA/IA - 30/60/10 3.0 MMA/EA/IA - 50/40/10 3.0 MMA/EA/IA - 30/60/10 3.0 S/BA/IA - 40/50/10 3.0 S/BA/IA - 60/30/10 3.0 S/MMA/EA/IA - 40/10/ 12.0 40/10 S/MMA/EA/IA - 30/20/ 40/10 7.0 MMA/BA/IA - 50/40/10 3.0 S/EA/IA - 40/50/10 10.0 s /Ea /ia - 60/30/10 22.0 S/MMA/EA/IA - 45/15/ 30/10 20.0 MMA/BA/IA - 50/40/10 3.0 S/EA/IA - 50/40/10 24.0 S/EA/IA - 45/40/15 23.0 s /Ba /ia - 60/30/10 23.O S/2-EHA/IA - 65/25/10 23.0 S/EA/IA - 55/40/5 22.0 S/EA/IA - 50/40/10 22.0 S/2-EHA/IA - 40/50/10 22.0 s /Ea /ia - 70/20/10 22.0 s /Ea /ia - 30/60/10 21.0 S/2-EHA/IA - 55/35/10 22.0 S/EA/IA - 50/40/10 21.0 62 100 100 100 100 100 100 78 71 90 100 100 94 90 100 100 100 100 98 100 100 100 100 100 96 100 100 1.102 1.143 1.128 1.049 1.062 1*053 1.051 1.048 -- 1.097 1.084 1.102 1.104 1.140 1.112 1.064 1.067 1.091 1.101 1.053 1.070 1.084 1.070 1.092 63 65 81 90 92 93 94 96 97 108 114 115 116 117 118 120 125 133 143 145 146 150 151 178 179 186 181 DUP030009269 10 Prom this table it can be seen that styrene/lA mixtures require 20 hours for 100$ conversion using the reaction procedure described in the experimental section. These styrene polymers, prepared at 50$ solids, can be stripped of isopropyl alcohol to higher solids before conversion to their aqueous ammonium solutions or con verted directly without stripping. Itaconic acid terpolymers {10$ IA) containing styrene require butyl cellosolve as a co-solvent to obtain clear, homogeneous, aqueous ammonia solutions. The amount of butyl cellosolve require is related to the styrene content of the polymer. Polymers containing 4'0$ styrene require 10$ butyl cellosolve while- those with 70$ styrene need 20$ of butyl cellosolve.. In contrast to the styrene systems, the methyl methacrylate/IA mixtures are polymerized to 100$ conversion in 3 hours. Furthermore, these polymers, as their ammonium salts, are completely miscible with water without the aid of organic solvents. These copolymers have been brought into solution with aqueous ammonia after all organic solvents were stripped off. This provides a definite cost advantage for these polymers which can overcome the lower initial cost of styrene. B. Properties of HMDA Crossllnked IA Copolymer Films Previous scouting work by J. C. Fang (I) established that the ammonium salt of a 40/50/10 terpolymer of styrene, ethyl acrylate and Itaconic acid crossllnked with hexamethylene diamine (HMDA) produced attractive coatings which had good adhesion to "Lucite" automotive enamel. The attractive advantages of a sealer less primer for "Lucite" led us to investigate the feasibility of using the diamine crossllnked itaconic acid terpolymers as a binder for a sheet metal primer. ` . Initial work' was directed at evaluating these polymers as clears to establish the approximately optimum monomer levels for cost/property balance. Styrene/ethyl aerylate/itaconic acid ter'polymers where chosen first because of cost, expected properties andr-their already demonstrated adhesion*'-to "Lucite"/ -- - 1. Effect of Copolymer Composition A series of S/EA/IA copolymers containing 10$ itaconic acid with S/EA ratios of 60/30, 50/40 and 40/50 were prepared to determine the effect of monomer ratios on flexibility, hardness, adhesion and solvent resistance. Evaluations of these polymers are recorded in Table III. _ DUP030009270 cq o a< o o QM O <C H0 H & O M M O <c W tE-Hh 3 pq fe O EH CO s 0 B & MEh 1 s ..-11--. CD 09 O ft O 09 4> 0) pc; 0 <t 43 c CD a> C > CD !--t rH O rN co f! 0) <4-1 x: H TJ * o T3 O 00 C PQ I rH C ,, 4 s tj o io b h c mp h o o p h Ph o c ij Ph Ph c s o p h o c j Pe.OOOPh OCJPh Ph OOPh Ph OOPOO IfN tA . mmmmmmmmmco t--oo moo mo n o oooo m mmmm m m m oo m oo ON ON ON ON CT\CO b- is- CJ\ ON ON IN-CO rH rH ON rH rH pH o o o Si- m CM a J* a) X5 > rH 03 O <3 09 s O rH cj! 1--1 Ph 0 O 0 00 rH o n m NO 43 rH X 3 XI -f1. _ 4 -o ft 0 0 fe p It &4 0 bO m 1 3k O CD O> a 1 3 1 m c 0 > p0 o oo C--NO ONCO ONCO ONCO a\C!NeO CJNO-rH ON ON rH rH oo oo ooo ooooo OO CO rH rH ON ON i--l rH ON r-1 H rH ON rH i--I i--It--I rH C H X Su *ao 3 ft Jxt rH 4 CM <4h <1) h rH 01 c 43 ft SCO X} 43 TJ 0) U 3 riHH <r4 + 403) o <0 c o *o a Jit 4 oa 3 (fl ffl Eh US C IXNCM n o mo m.=t- o j o o rH^ooNovo mcovo c m.=j - c m mmmcM ia n o -t t mm-=r c o io h ^- mm rH rH rH rH rH rH rH rH rH rH rH rH rH rH rH rH 4 c p. X! 09r-s 4 H o. C <tH S rH <CVDH rDH.JH U SO 0)0 0 PH O Ph U 11 II bO omo omo omo omoi oo tmo o c-moo n a o o t-m r-t t~i r-t a h s 0. 4 3 03 rl s J2 C H 43 fC OOh I o 3 o o O .rH O r> rH 4> rH O O t H (h P. x: 0 <T4 in in 43 3 CO +> t <r =' <r* o -=* o NO om w> tC X! ^J Eh X! 4> XI CQ O o. c eo O tH O 43 <s MM CO CO o * 09 TJ 4 ft 4 Is' o _ O TJ OC o rH 0043 1m I IIIIIII IIIIIII NO IN- O |K>^ 0 0 00 00 ON ON 00 t j =r -4* .. sf 1--! rH O jC -P 'w* 0 b---- " -- b"~-- -- s isas-i s. .- = = = mm 0 CM CM CM CM .. 1 l 1 1 1 1 00 JS & IS is PS p c DUP030009271 12 Statistical analysis of these data by S. C. Horning indicate that: 1) At equal levels of HMDA there is a consistent, but small decrease in hardness as the styrene content changes from 60 to 50 to 40 parts. 2) The amount of styrene had no consistent effect on impact, bend, adhesion or solvent resistance. A second series of polymers, listed in Table 17, were prepared and evaluated to determine the effect of butyl acrylate and 2-ethyl hexyl acrylate on film properties of styrene/ itaconic acid copolymers. These polymers generally did not possess properties significantly different from those evaluated in Table III. Poly mers W-27496 and W-27499, which contain 2-ethyl hexyl acrylate, had poorer water solubility as their ammonium salts than the other polymers. The S/EA/IA and S/BA/IA terpolymers offer the best balance of properties with the S/EA/IA system possessing a possible cost advantage. Polymers W-27502-1 (S/&A/IA - 70/20/10 - 100$th HMDA) and W-27503 (S/EA/IA - 30/60/10 - 100$-Th. HMDA) were prepared to show that there are differences In flexibility between high and low content styrene copolymers. As expected there Is a difference in flexibility between these polymers with the 30/60/10 terpolymer both softer and more flexible. Note also the poorer solvent resistance of this polymer. a. Itaconic Acid Content Most of the polymers evaluated in Tables III and IV contained 10$ Itaconic acid. Two polymers, -27492 and W-27497, were prepared containing 15$ and 5$ IA respectively, to determine the effect. If any, of itaconic acid concentration on polymer properties. Polymer W-27492 containing 15$ IA had poor flexi bility when crosslinked with 100$ of theoretical HMDA. At other levels of HMDA it had equivalent properties. Polymer W-27497 with 5$ IA had poor solvent resistance at all levels of HMDA. This polymer as its ammonium salt also had poor water solubility. From this It appears that 10$ itaconic acid is the optimum level. b. Degree of Crosslinking The effect of degree of crosslinking with HMDA on film properties such as hardness, flexibility, adhesion and solvent resistance was also studied on the polymers listed in Tables III and XV. DUP030009272 54 p 02 03 43 , >IJ X C rH fl > I I--I fi O O m <sj <p CP 0 O^tUOOCHCMOtX >> 04 CL)04 fe X * * W !> Ph > t> Ol j O^c UO t >>>> ci> O C4 CM Oi ft| c m pl , o * >>>> > <5h H S3 O rH JC O I <v ' i * frt. o O TJ 00 S3 |PQ H .S3 S+ S *0 I I S3 O |o feotsofeodjixi : CM o ooo VO O 00 VO <\1 CVJ 04 CVJ LTv o O 0 oo o CF\r--1 rH ONVO ITliHVO oooo * * oot-co t--vo mm ooocuoo o*ooinoo CVI 0OCVI-=J-tACO oooom * * o C-ONC'-VOQO rH o*ooo m o mmt--vo oooo mo mo CO CO 00 VQ oooo H rl rl rl mo m c o o no no o > lo o Q m mo o o t * o oommo rH .=* ONCJNCOCOVOCO oo mooooooco m o o o ON rH rH ON s o ra Xu VO CM 04 04 04 t>-C--CVl * vo*-=4"-s*r t-- t--oo-\ m 0400 co vo * 3 irv=f-=t-v0 murv=t- on on o j m^f vo * * *0 -=4" E-t S3 rH rH rH i--I r--I rH rH rH r-l rl H rl rl O rH CM rH r--l u 3 4> O 3U P 00 1 o 2. so O *H O -P oa o oo o o mo o o rH t--mo m-H o oo OO OO iTVrH O LfVrHO m oo rH 'x o= = o= in <! m sf < m vo Os S* s< mo m =4" \ 4j <C < J-H JH <4! >H \<% 11 II A it Is<* = ( M = = \ * B I CO w CO X ^VJ CO \ CO CVJ ON *4*B = = t04 1 3! m VO o\ ov -=1* c-~= bcvi c v j t1 35 35 O <S CQ O (fill N)M ON ON ON =r -S3" = = |> = t>CVI 04 1< 35 35 oo omori OrH roH \ o ^4" \ o m TO HH CO <50 o on 0 on rHJ- onfr- 1 CVS o* 3s 13 - T3 X ,3 m ra o* PO o rH on rH OI C 23 Qi O fe Oo rH O o on p ,, H f*J u - oo c on o o *3 o .O "D -O t C SPhu ra Sh o 3 *rl ra .li, po SO rHrl rSH ^O4" *H <M K rH <h m S 04 DUP030009273 Prom this study it can be seen that: 1) at least 75$ of the theoretical amount of HMDA is required for good solvent resistance 2) HMDA crosslinking provides a slight signifi cant improvement in flexibility, but the amount used is without effect. Addition of HMDA also provides more cohesive (less brittle) films than those obtained in its absence. Por these reasons it was believed that crosslinking with 100$ of theoreti cal HMDA would provide optimum properties. '2` - Pop Bottle Polymers Versus Plash Polymers As mentioned previously itaconic acid copolymers were originally prepared in pop bottles. In going to larger scale flash polymers it was necessary to demonstrate if differences exist between pop bottles polymers prepared in butyl cellosolve and Identical polymers prepared In refluxing Isopropanol. In Table V polymer W-27506 (Rel. Vis. - 1.038), prepared in pop bottles in butyl cellosolve is compared with polymer W-27593 (Rel. Vise, = I.067) prepared in refluxing Isopropanol. These polymers had essentially Identical film properties indicating that polymers prepared in refluxing isopropanol are equivalent to pop bottle polymers of the same composition. DUP030009274  -p 03 H 03 CD CD 04 G 0) -P 1--1 C CD X > r-l 1 CD O CD C CO O O < +3 CD ft H , G1 -- 15 cScSO ft, 04 Pc ftOO Pc 04 04 ft ft O ft O O ft ftft ft ft ft tA r-l OIOO OSOSOS A t--OS OSOQ rH OS o O 00 rH co O PS CGD $ aI C rH O IS O CVl-=f ino o m CO 0-0- ino o ao s c q OOO^COOO o*o a OSi--I OS AO AO A A OS 0-00 CO 00 00 3 o O. o o t 8a > o oo 9 9, Er* o M oG -aI cq 8 X ^3 *i CCt ca CD o c < 4 gr CD G H s 0 aEt M ri Eh ft 1 03 O g-c so O rt O -P SO SO VO AAA 00 OSCO o as as as o s h o s rl4-OS =f oo a i--I rH CU SO A A O CM O r-l r-l gff Q <C ft p 0 04 04 04 *3l 04 ' 04 - ft^> O < OO O iH Q A r-l r-l OO AOA osoocoassoso osososasosos AQ O USH H IH: rH^tVO O-A A H rl rl H rlH <$ a I rH 0o4 C0 CO 00--00 H3 03 CO Ir-l CIM ><lrv=4i- rH 04 rH 04 PS A 04 0O-=i- A SO OSO OO O o CD J=l- A AA A A O 0-0- 0-0- O- '|Sw o CV1 04 = CVI 04 04= = 04 o tI SB 3s tSI SBI I 5= l--1 a A o p <a CO r-l CD G at a. _ 04 Oo oo rH O A CD P X H GSo X3 A G O TJ A CD X C a) OA >0 X3 CD C t>rtt g a Or to 00 CD CD Jrr*f GO CD *H JS -P 03 aa rH rH rl rl Pc ft CD G H a cd at G rH 4-4 >>a P> aj O -H GTO a. CD <H H G -a o rl O a o t> <0 G rH H --! bO 'O B fit CD CD t H C G T3 CD CD l rH rH ** }* hen p. -G > O -PAG <D p. a si cct rH X <! O CD 04 P. SI Q S) 11 11 ft l <$ i 55* ft ft AO S n04 a aph) P a ir Good DUP030009275 - 16 XBV Effect of Casting Solvent on Film Properties Polymer W-27505 (S/EA/IA - 50/40/10) was prepared and divided into two parts (A & B) to establish if polymers cast from anhydrous organic media have different properties than those cast from aqueous organic solutions. Part A was converted to the triethyl ammonium quarternary salt and let down with toluene while part B was converted to its aqueous ammonium salt. HMDA was added at 50 and 100$ of theoretical levels to both parts. Evaluation of these vehicles, recorded in Table V, gave identical film properties for these polymers indicating that a wide choice of solvent media is possible and that the ultimate choice of solvent will depend on polymer composition and end use. it- High Styrene Copolymers Crosslinked with Long Chain* 1 Diamines ____ _____ ____ W-27502, a S/EA/IA - 70/20/10 copolymer, was pre pared to show whether high styrene copolymers could be made more flexible using long chain diamines. Polypropylene glycol diamine and 3,3 '-diaminodipropylamine, HN(CH2CH2CH2NH2)2 were used. Table V compares the use of these diamines with HMDA (See W-275021,2,3 & 4). These data show that high styrene containing polymers can be made more flexible with considerable sacrifice in hardness and solvent resistance by employing long chain diamines as crosslinking agents. The optimum chain length of the diamine depends, of course, on the styrene content of the polymer and appears to be between HMDA and PPGDA. C. ia Copolyfrfer/HMDA Sheet. Metal -Primer 1. Formulation In conjunction with the evaluation of clears of diamine crosslinked itaconic acid copolymers, several polymer compositions were formulated as sheet metal primers. The polymers selected were; W-27488 S/MMA/EA/IA 45/15/30/10 W-27494 S/EA/IA 50/40/10 W-27501 S/BA/IA 60/30/10 all crosslinked with 100$ of theoretical amount of HMDA. Pigmen tation of W-27488 and W-27494 (See experimental section or Table VI) used the formulation developed by D. Flitter (2,3,4) as the best for water borne sheet metal primers. Critical pigment volume content (CPVC) calculations (N.B. 7362, p. 162) indicated, how ever, that these formulations were oyer the critical pigment volume of W-138 (micronized talc). Primer W-27501 was formulated using additional W-1008 (aluminum silicate) to replace W-138. Calcula tions indicated this formulation was well below CPVC. Table VI is a tabulation of the pigments used in 64-1690, W-27488, W-27494 and W-27501. DUP030009276 - 17 TABLE VI TABULATION OF PIGMENTS IN 64-1690, W-27494 AND V/-27501 mtasmaBsssPasiBgsamstsmeKnamt aBsasssssmasam^ Code I 64-1690 Weight Weight % Of $> Of Total Total PigmentBsBaaaSgMtotgglgiadeaesgg Weight Of Gilder *s Whiting -W-90 Carbon Black Pellets W-224 C.P. Zinc Yellow W-609 85.54 9.28 5.18 Totals 100.00 43.03 .4.67 2.60 50.30 25.41 2.80 I.54 29.75 $0.01 .19 .29 II W-27488 and W-27494 Lead Silico- KW-5781 chromate Molacco Black W-222 Micronized Talc. W-138 Aluminum Silicate W-1008 4.58 4.46 30.29 60.67 Totals 100.00 III W-27501 2.46 2.39 16.26 32.59 53.70 0.98 .94 6.38 12.79 21.09 0.212 .136 .060 .040 Lead Silico- KW-5781 4.58 ` chromate Molacco Black W-222 4.46 ; Aluminum Silicate W-1008 90.96 Totals 100.00 2.46 2.39 48.85 53.70 1.01 .99 20.19 22.19 0.212 .136 .040 DUP030009277 O 0 o 3 =0 OP O0 i--t *H 0 X0 3 3P P0 3 CtiTJ PP C P0 O0 T5 0 3 X3 p 0 3P 0 s: 01 0 3P PO0 HO <Mrl HH 30 P PH s XS H _ 0> PH OH0 Sofl 30 xs 0Eh 0 -P Pm 00P00 O P D. 3 O 03 F le x ib ilit y , Hardness and Adhesion P -P P sc 1-t <1> o o>o IT\P IS* 0= 1 PCVI 00 JjS P 00 o >3 0 3 3 0P 0 3= XS UX3 OV 0 3 P- P 0 C- CVI HS 1 tsX 3s P 3 PP P3 CO PQ 00 P= =* X SP CVI P 0 1 <3 3 SB P o.. <6(800 0 B ra-^> cvi a P3p0 o3 ffl 03} P0) PS at o f>fl PO > at ) gsw - 18 * 0 ta ON rH t*r tI tXNOO lACO tno rH 3 3 <L> <3 O3 XOS oo o o3 P 3 *rH XoS Xo) XS *o 00oooo 0 > P60 O CD CD ffl &l CD CD CD CD tP 0 3m 0 P Se *3 < 0&| O O at P P o rH [*-- OH O O rH O rH xa P Eh 0o CO fi s (3 ffa P ta QP t 4 00 P 0 COCO in toco XJCO I I o o(X p xs 03 3 i P a3 3 rH 0 rH P0 0a 00 P0 0 pr-s 0 0 XJ 0 PP 0 0 >S<iH P rH O 3 3 003 03 t CD P CD 3 00 CD o3j -oP o p ~r o ON O o\o rH O 3 P O > 0P PP 3 POao- P0a*-C3^| P3> I--1 o 03 2 r03t) >; X rH C--- O rt offl QV t** H (*! Ooon p rH 0 3 0 Pl3C* 3 O 3 OP 00 0 0 fOlrH 0S o ID COPO 3 CD ffl I 3 i-l 0 oo a cvi cvi o o rH C-- OP I I o o O O a O o rH t>- rH E-- rt S X ocn o X0 0 303 P Pa Ik P0 p>0 po 03 XS . O hPe ffl P P O 0> a P 03 P O p o ffl 0 P. M a w f ffi o 3o lo oo a vo VO m o 0000 oo QOoo a Oto to vo a ovo m m o man is*.is* X> S-X) CO 0 3 0 S 0 ft taH 03 P P 0 3 3 OP 3 0= K 0 0 0 >3 0 3 <3 P 3 3 P P 3 ft 3 0P 3 0 B 0 P O a 0. 0 mP CO 3* p O , S U a o rH O M Pi o30in ta p I ff) P B0 030i0n < Pra N oto S-P" 3O. _ P* I s-o o OCO to P toovPp-ointop p0 PlOiVlOtCVI 3 0 a t o=t*cpotvorvo^vr coto b~ CO VO 00 p VO rH rHP- Q3> 0* o 8* CVJ OVP 1 1O Pov* arH? P3 <Xo < & oOVioQ_ Wo X? vo vo a P3 prHI* PrHI" fft vo vo P0 aH3 3 0.... 'P 0 DUP030009278 - 19 From these data It can be seen that the experimental primers are essentially equivalent to the controls in the pro perties evaluated. b. Salt Spray Resistance Salt spray resistance of primers W-27488., W-27494 and W-27501 was determined using 64-1690 as the control. These primers were over "Bonderite 100" and were not topcoated. TABLE VIII SALT SPRAY RESISTANCE OF EXPERIMENTAL SHEET METAL PRIMERS Film. Bake Primer Thick. Min. x F. T2S 64-1690 0.3-0.7 25x400 None* W-27488 0.5 30x300 1* W-27494 0.5 30x300 11 W-27501 0.5 30x300 If Hours in Salt spray -33 8B0 Lost adh Failed - 1/32"* 1/32" 1/32* 1/32" Blistering losing adh. Blistering losing adh. 1/8" lost adhesion - * Total Creepage in inches from x scored on panel. Table VIII shows the experimental primers have better salt spray resistance than 64-1690 control with primers w-27488 and W-27494 having excellent salt spray resistance. c. Blister Resistance Blister Resistance of experimental primers W-27488^ W-27494 and W-27501 topcoated with nLucite" and "Dulux 100'" was determined in humidity cabinet against standard ''Dulux'1 and "Lucite" controls. Blister resistance of experimental primers topcoated with "Dulux 100" was very good. No blistering was observed up to 700 hours exposure while the "Dulux" control had general light blistering on 200 hours exposure. DUP030009279 20 "Lucite" topcoated experimental primers, however, showed intercoat blistering at 120 hours. Blistering became very severe on continued exposure. The "Lucite" control (64-1690/ 881-94184/865-050) had a perfect rating after TOO hours exposure. To establish whether the poor blister resistance of "Lucite" topcoated experimental primers was due to pigmentation or a characteristic of the itaconic acid copolymers, a series of polymer clears as ammonium salts and erosslinked with HMDA were prepared. These systems are listed below: Code W-27499 ft ft W-27493 it W-27466 W-27495 II tf W-27 496 ft W-27497 u It No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Structure S/2-EHA/IA 11 It S/EA/IA It MMA/EA/IA S/BA/IA 11 if S/2-EHA/IA II It S/EA/IA It If Composition 40/5ft 0/10 It 50/40/10 It 50/40/10 60/30/10 II 11 65/25/10 II II 55/40/5 It II % HMDA 0 50 100 50 100 100 0 50 100 0 50 100 0 50 100 These vehicles ware topcoated with "Lucite" and exposed in humidity cabinet to determine effect of structure and crosslinking on blister resistance. Pine blistering was observed on some panels in 48 hours and on all in 100 hours. Heavy blistering and loss of adhesion was observed after 312 hours exposure. Poor blister resistance appeared to be characteristic of the IA copolymers when topcoated with "Lucite" and was inde pendent of their monomer ratios or degree of crosslinking. d. Cost Mill cost calculations were made by G. Lackman for vehicle preparation and primer formulation, Regular Philadelphia' or Flint costs were used except where noted. DUP030009280 - 21 - Primer Mill Cost/Gal. 64-1690 64-1690 W-27494 W-27494* W-27494* 881-94184 881-94184 $1.65 (Phila.) 1.495(Flint) 1.884(Phila.) 1.775(Phila.) 1.663(Flint) 2.205(Flint) 2.33(Phila.) Vol. Solids io 42.1 42.1 24.2 24.2 24.2 22.0 22.0 Th.Coverage Mill Cost/ Mil.. Sq.Ft. Mil.Sq. Ft. 673 673 387 387 387 352 352 $0.00245 .00222 .00487 .00458 .00431 .00627 .00664 * Calculated using cost of $0.20/lb. for ethyl acrylate Using these costs, one arrives at the following costs for the experimental primer and current "Lucite" primer-sealer combination.. Cost of Exp. Sealerless Primer W-27494 At 0.5 Mil $ 0.00229/sq.ft. Cost of Primer/Sealer Combination = E-.mi <5.>3b3/3q.ft. These figures show that although experimental primer W-27494 is not competitive in cost with 64-1690 it is less expensive per sq. ft. than the primer - sealer combination presently employed for "Lucite" automotive lacquer. D. Comparison of IA Copolymer/HMDA System With Commercially Available Water Soluble Systems J ** A search of the technical literature was conducted with the aid of H. Stauffer to ascertain that presently available, competitive water soluble resins do not possess film properties equal to our water dilutable ltaconic acid copolymers. Only baking systems were selected as these would be most competitive with the IA copolymers. Table IX below lists all the available resins uncovered. New resins will be investigated as they become available. DUP030009281 22 TABLE IX COMMERCIALLY AVAILABLE WATER SOLUBLE SYSTEMS Resin Manufacturer Composition Cost/Lb. Solids SMA lOOOA Texas Butadiene Styrene-Maleic anhydride $0.50 and Chemical Co. copolymer. Mol. Wt,, = 1000 1 100$ solids | Carboset 531 B, P. Goodrich Thermosetting Acrylic Chemical Co. 25$ solids I.50 ; Melaqua 600 American Cyanamid Melamine crosslinked acrylic. 50$ solids 0.90 Gantre z AN- General Aniline Methyl vinyl ether - and Film. Maleic anhydride copoly mer . 100$ solids 1.25 Cargill 750 Cargill Incorp. Thermosetting alkyd. Requires drier. 50$ solids 0.468 Arolon 304 Archer Daniels Midland Water soluble alkyd. Requires drier. 43$ solids. 0.63 Arolon 1001 Archer Daniels Composition unknown. Midland 45$ solids 0.92 Resydrol P-411 Cray Valley Prod.Alkyd crosslinked with Ltd. Licensed to phenolic. 67$ solids Hercules Powder. Sold as Polymer A-411 0.61 Epok A-1700 British Resin Products Ltd. Composition unknown. 43-46$ solids. - Resin C-50 Spencer Chemi cal Co. Non-oil modified alkyd. 40$ solids. O.65-.90 Aqualon 200 Benson Process Long Oil alkyd. 50$ Eng. Co. solids 0.30 DUP030009282 - 23 - Of these resins, AroXon 1001, Arolon 304, Melaqua 600, Carboset 531, Cargill 750 and SMA 1000A were evaluated as clears for hardness, flexibility, adhesion and solvent resistance. This evaluation established that two them them, Melaqua 600 and Carbo set 531, have film properties equal to the diamine crosslinked IA copolymers. Further evaluation of Melaqua 600 and Carboset 531 as primers showed them to have poor adhesion to "Lucite" and "Dalux 100" automotive topcoats. Salt spray resistance of these resins on bonderite 100 was also found to be poor compared to a crosslinked S/EA/IA vehicle. The remaining resins, listed in Table XI, were not available in time for this evaluation, but will be evaluated in the near future along with other newly available resins. EXPERIMENTAL Bead Polymerization of MMA/BA/IA (See Table X). Materials: Methyl methacrylate Butyl Acrylate Itaconic Acid Water Triton X-100 (5$ aqueous) Benzoyl Peroxide 100 g. 40 60 200 30 2 H-428 Rohm & Haas Lot # D-201 Eastman Kodak #2690 Tap Rohm & Haas Cadet Chemical Procedure: (N.B. 7362, p. 35; N.B. 4424, p. 18.' Code W-27414) A 3-liter 3 necked flask fitted with condenser, ther mometer, and stainless steel stirrer was charged with the above ingredients. While stirring rapidly, the reaction mixture was heated to reflux, 87C., in 20 minutes. After 30 minutes total reaction time an exotherm was observed, reaching a peak tempera ture of 98C. in 8 minutes. During this time bead formation was noted. After 79 minutes the reaction temperature had fallen to 95 Cold Water (300 cc) was added after 109 minutes. The beads were filtered, washed 3 times with cold water and dried under vacuum. Wt. obt. I46g. Conv. 73$ Solids 95.5$ Acid No. 85 (equal to 9-4g. IA/100 g. polymer). Rel. Vise. 1.20 DUP030009283 24 - TABLE X BEAD POLYMERIZATIONS Code W-27404 -27407 W-27408 -27411 W-27414 W-27418 W-27425 -27426 -27427 -27431 -27432 Structure Monomer Composi tion $ IA by $ Conver- Rel. Acid No., sion Vise. N.B. 7362 Page MMA/BA/IA MMA/BA/IA MMA/BA/IA MMA/BA/IA MMA/BA/IA MMA/BA/IA MMA/BA/IA MMA/BA/IA MMA/BA/IA MMA/BA/IA MMA/BA/IA 50/40/10 50/40/10 50/40/30 50/20/30 50/20/30 50/20/30 50/40/30 50/40/30 50/40/30 50/40/30 50/40/30 0.8 1.5 9.0 8.5 9.4 27.8* 5.0 14.2*** 9.0 8.2 9.2 90 63 75 70 1.23 70 1.20 70 - 1.171 7 1.182 63 69 1.183 70 1.14 20 24 26 31 35 41 48 49 51 56 57 ^ Polymerized in the presence of Hd/ Apparently some was incorporated in bead. ** Polymerized in presence of (NH4) H2PO2... Solution Polymerization of S/EA/IA Materials: Styrene Ethyl Acrylate Itaconic Acid Isopropyl Alcohol Butyl cellosolve Benzoyl Peroxide 500g. 400 100 800 200 15 H-710 Rohm & Haas (H-721) Charles Pfizer & Co. #G.62640 H-69 H-224 Cadet Chemical Procedure: (N.B. 7362, p. 125i N.B. 4424, p. 126. Code W-27490) A 5-Hter 3 necked flask fitted with stainless steel stirrer, condenser and thermometer was charged with styrene, ethyl acrylate, itaconic acid, butyl cellosolve, isopropyl alcohol, 5 g. of benzoyl peroxide and heated to reflux. Benzoyl peroxide (5 g.) was added after 3 and 6 hours total reaction time. The reaction was refluxed a total of 24 hours then cooled to room temperature. Solids = 51$g, Conversion 100$, Rel. Vise. 1.112. DUP030009284 - 25 Solution Polymerization of MMA/BA/IA Materials: Methyl methacrylate Butyl acrylate Itaconie acid Butyl Cellosolve Isopropyl alcohol Benzoyl peroxide 500 g. 400 100 200 800 10 H-428, M-854 Rohm & Haas D-203 Pfizer Reagent G-62640 H-224 H-69 Cadet Chemical Procedure: (N.B. 7362, p. 120 Code -27489) The ingredients were charged to a 5-liter 3 necked flask fitted with condenser, stainless steel stirrer and thermometer. Mixture was heated to reflux, refluxed for three hours, then cooled to room temperature. Solids * 50.0$, Conversion = 100$. Conversion to ammonium salt was accomplished by adding 88 g. of 30$ aqueous ammonia in 824 g. of water to above polymer solution with rapid stirring resulting in a clear, pale yellow solution. A diamine-modified solution was obtained by slowly adding 88.6 g. of 50$ aqueous hexamethylene diamine with rapid agitation. Solids * 26$, Solids/Viscosity Relationship (N.B. 7362, p. 81, 88-91) Materials: -27455 MMA/BA/IA - 55/40/5 - Rel. Vise. 1.143 -27463 MMA/BA/IA - 50/40/10 - Rel. Vise. 1.143 Procedure: The two polymers above were prepared in isopropyl alcohol at 55$ solids. After conversion to their ammonium salts, they were reduced to 25$ solids with water. Their solids/viscosity relation ship was then determined using viscosity tubes. Continued reduction of solids with water gave the following data. See also plots X & XI. DUP030009285 Solids 24.0 23.5 23.0 22.5 22.0 21.0 20.0 10.0 W-27455 Viscosity 6.H. z-4 Z-l M A-l A-l A-2 1/4 LA-3 A-5 - 26 Poises 63.40 27.00 3.25 .32 .32 .22 .124 .005 Solids 25.0 24.0 23.5 23.0 22.5 22.0 21.0 20.0 19.0 18*0 W-27463 Viscosity G.H. Z-6 Z-6 Z-6 z-6 Z-6 Z-4 Y N B A-l Poises 148.00 148.00 148.00 148.00 98.50 63.40 17.60 3.40 .65 .32 DUP030009286 Pi.OT& X *JET 27- WSCQStTy CPotsesd DUP030009287 These data show that both polymers undergo a sharp viscosity drop on reduction with water at 20-24# solids. It appears that polymers containing 5# IA undergo this viscosity drop at higher solids than polymers containing 10# IA. These results are not unexpected' since steep solids/viscosity relationships are common to polyelectrolytes and are apparently due to ionic inter action. Experimental Automotive Sheet Metal Primer - W-27494 Materials; S/EA/IA - 50/40/10 as NH4+ salt. Butyl Cellosolve Hexamethylene diamine Lead Sillcochromate Molacco Black Micron!zed Talc. Aluminum Silicate 1600 g. (24.8# solids) 215.0 37.4 22.2 21.6 146.8 294.4 W-27493 H-224 M-50 KW-5781 W-222 W-138 W-1008 Procedure: (N.B. 7362, p. 137, Code w^27494) Above Ingredients were added to one gallon pebble mill, mixed, two quarts of pebbles added and the mill sealed and rolled for 8 days. The ground primer was removed from mill and filtered into gallon can. Fineness P/B Vol. Solids # Solids PVC Gal. Wt. - less than 0.5 mil - 116/100 - 24,2# mm 39# - 38# - 9.53 lb./gal. Experimental Automotive Sheet Metal Primer - W-27501 Materials: S/BA/IA - 60/30/10 as NH4+ salt Hexamethylene diamine Lead Sillcochromate Molacco Block Aluminum Silicate 1666 g .(24.2# solids) 35.1 22.2 21.6 441.2 W-27495 mm KW5781 W-222 W-1008 DUP030009288 ~ 29 -- Procedure; (N.B. 7362, p. 164, Code -W-27501) The above ingredients were ground In a gallon porcelain mill containing two quarts of pebbles for 4 days. Fineness P/B Vol. Solid * Solids PVC Gal. Wt. -- less than 0.! - 116/100 - 29* - 41.3* - 34.2* - 9.61* lb/gal DU P030009289 REFERENCES Included in the following are references given in the text of this report and those referred to in the course of this investigation. 1) J. C. Fang, "Water Soluble Polymers as Primary Binders for Finishes" R-61-192) D. Flitter, "Water Borne Sheet Metal Primer" R-59-61 3) D. Flitter, "Water Borne Sheet Metal Primer1- II" r -60-45 4) D. Flitter, "Water Borne Sheet Metal Primer - III" R-6O-5I 5) D,, Glenn, "Formable Finishes for Strip Coatings" R-61-2 6) M. Greif & R. W. Laurrell, "Developmeht of Primer Surfacer for Use under "Buco" and "Lucite" R-57-14. 7) M. Greif, "Body Primer Surfacer for use with "Lucite" Acrylic Lacquer without Sealer" R-57-64. 8) M. Greif, "Water Borne Automotive Body Primer," R-59-72, 9) M. Greif, "Water Borne Vehicles for use as Primers for `Lucite1 Acrylic Lacquer" R-60-41. 10) M. Greif, "Water Borne Automotive Primer for "Lucite" Acrylic Lacquer" R-6O-56. DUP030009290