Document GkzwOMVqZvKy6vVBgQg3pjJY

R-61-19 INDEXED CC: C. W. Theobald, Wilm. F&F )ln J. A. Klacsmarm, " " )Turn P. B. Cochran D. MeBurney, Tl J. W. Nestor R. B. Davis, C. F. Kalb, ") " )In Turn ") J. C. Richards, Newburgh 0. H, Bullitt, Jr., Exp. Sta. L. G. Wise, Exp. Station J. P. MeAndrews, Flint a File: 1865 E. I. d.u Pont de Nemours & Company, Inc. F. & F., Research Division Marshall Laboratory Research Report WATER SOLUBLE POLYMERS AS PRIMARY BINDERS FOR FINISHES Date Issued 1 Period Covered : Project No. : Previous Reports Notebook Nos. March 22, 1961 Feb. 19* i960 to Dee. 30, P-1502 (Formerly P-3601) i960 The acetate salt of the above polymer appears to show projnlse as the room temperature convertible system. Prom the literature information (Reference 6), dimethyl sulfide has been shown to react with beta-propiolaetone to give dimethyl-beta-propiothetin 3alts In good yield. DUP030009189 ABSTRACT TABLE OF CONTENTS PAGE NO. ABBREVIATIONS & FORMULAS INTRODUCTION----------------------------------------------------------------------------------- 1 OBJECTIVES--------------------------------------------------------------------------------------- 1 SUMMARY AND CONCLUSIONS------------------------------------------------------- 1 &2 ACTION TAKEN OR PROPOSED------------------------------------------- PATENT INFORMATION----------------------------------------------------------------- 2&3 PUBLICATION STATUS----------------------------------------------------------------------- 3 DISCUSSION-------------------- --------- -------------------------------------------------- 4 to 7 Evaluation Result of Itaconic Acid Terpolymers Cross-linked with Diamines---------------------------------------------- 8 Preparation of Experimental Automotive Sheet Primer-------------------- -------------- ---------------- --------------------------- 8&9 Preparation of Experimental Appliance Enamel----- 9 & 10 Scale Up of Styrene/Ethyl Acrylate/itaconic Acid Terpolymers---------------------------------------------------------------- 10 Trimethylsulfonlum Salt of 50/50 Styrene/ Itaconic Acid Copolymer----------------------------------------------- 11 Preparation of 2-Ethylthioethyl Methacrylate-- 11 & 12 Preparation of Water-Soluble Sulfonium Polymers Derived from Poly-2-Ethylthioethyl Methacrylate-- A. With Methyl Iodide------------------------------------------- 12 B. With Methyl Sulfate------------------------------ 13 C. Convertible Sulfonium Acetate Polymer-- 13 Attempted Reaction of Poly-2-Ethylthioethyl Methacrylate with Beta-Propiolactone--------------------------- 13 2 DUP030009190 Table of Contents (Cont'd,) Page No. LITERATURE REFERENCES----------------------------------------------------------- 14 TABLE I Itaeonle Acid Terpolymers---------------------------------- 15 & 16 TABLE II Evaluation of Automotive Sheet Metal Primer---------- -------------- ----------------------------------------- 17 DUP0300091 91 ABSTRACT Various routes to water-soluble polymers useful as primary film formers have been investigated. Ammonium salts of itaconlc acid terpolymers were water soluble at lowest carboxyl content (5$) and converted to alkali-insoluble polylmides on baking. Using diamines as cross-linking agents, these soluble terpolymers gave films with attractive physical properties. DUP030009192 ABBREVIATIONS & PORMUIAS MMA Methyl Methacrylate BA Butyl Acrylate EA Ethyl Acrylate IA Itaconlc Acid S Styrene AN Acrylonitrile V54 Alcohol 2-Vinyl-l,3-dloxolane-4~butanol PA Fumaric Acid MA Maleic Anhydride 2-EHA 2-Ethylhexyl . Acrylate DUP030009193 WATER-SOLUBLE POLYMERS AS PRIMARY BINDERS FOR FINISHES INTRODUCTION: The rapidly growing demand and large potential market for water-based finishes indicates successful development of new water-based coatings with competitive advantages should provide F. & F. with increased sales and profits. This project was started to scout various routes to new types of water-soluble polymers useful as primary film formers for finishes. This Research Report deals with the progress made In this field. Meanwhile, a systematic study of these water-soluble polymers as adjuvants for emulsion latlees has also been started and will be reported separately. OBJECTIVES: The main objective has been to scout broadly various routes to new water-soluble polymers useful as primary filmformers and to develop coating systems with competitive advantages over conventional finishes. SUMMARY AND CONCLUSIONS: Itaconic acid acrylic terpolymers as ammonium salts continue to show most promise in providing water solubility at lowest carboxyl content (5$) and conversion to alkali-insoluble polyimides on baking. Using diamines as cross-linking agents, films with attractive physical properties and high degree of water resistance have been obtained. Itaconic acid copolymers and terpolymers of methyl methacrylate, ethyl and butyl acrylates, acrylonitrile and styrene have been made and used as the polymer backbone. Diamines such as ethylene diamine, bexamethylene diamine, 2,4-diaminotoluene and bis(4 -aminocyclohexyl)methane have been used for cross-linking. Diamine-terminated polyamides such as N^CHgCHgNHCOCCHgLNHg made by the reaction of caprolactam and ethylene diamine have also been used to obtain an attractive balance of flexibility and hardness. Typical primer and topcoat formulations have been evaluated and show attractive hardness/flexibility balances. An automotive sheet metal primer formulation based on ammonium salts of 40/50/10 styrene/ethyl acrylate/itaconic acid and hexaraethylene diamine has shown excellent corrosion resistance and direct adhesion to "Lueiteff* Acrylic Lacquer without sealer. -Registered Du Pont Trademark DUP030009194 2 The same vehicle also provides promising formulation for aluminum strip coatings, and appliance finishes. These leads will be investigated further in continuing work. A search for water-soluble polymers that convert to insoluble films at ambient temperature has been made. Watersoluble sulfonium type polymers derived from poly-2-ethylthioethyl methacrylate and the V54 modified ammonia-soluble polymers such as MMA/2 - EHA/Male 1c -V54 half ester/AA interpolymers _ (30/60/5/5) have shown promise in early tests and are being studied further under P-1201. Itaconic acid terpolymers also formed water-soluble trimethylsulfonium salts which were converted to the corres ponding methyl esters on low bakes. However, room temperature conversion reactions were very slow and did not yield water in sensitive films. The by-product (dimethyl sulfide) evolved during baking was odorous and this would, limit the general usefulness of these trimethylsulfonium salts in finishes. ACTION TAKEN OR PROPOSED: The writer has been reassigned to another project (P-1204). Further evaluation and scale up of the itaconic acid terpolymers and diamine modified vehicles will be continued. PATENT INFORMATION: The prior art and known patents in the field of water-soluble polymers up to December, 1958* were summarised in Research Report R-59-35 A recent competitive patent, U.S. 2,906,724 (9/29/59) issued to American Cyanamid Company claimed a composition of a water-soluble potentially thermosetting polymethyl ether of a polymethylol melamine and a water-soluble ammonium salt of an acrylic copolymer of an alpha, beta-ethylenic unsaturated carboxylic acid. PATENT PROTECTION: FFD-1699 covers water-soluble ammonium salts of itaconic acid terpolymers as lacquer compositions. DUP0300091 95 -3- FFD-1713 covers polyalkylthioethyl methacrylates and their water-soluble sulfonium derivatives. FFD-171^ covers methaeryloxyethyloxazolidines, monomers and polymers thereof. FFD-1719 covers itaconic acid terpolymers and diamines. PUBLICATION STATUS: The work on water-soluble sulfonium polymers based on 2-ethyl thioethyl methacrylate will be proposed for publication after the patent application has been filed. 9' SatfVH ^ s- 'W C <><ns*4>C 3 ^7iZfuQ f<lCf DUP030009196 -4- DISCUSSION: Water-soluble polymers have long been recognized to have attractive possibilities as vehicles for finishes. The major objective of this research program has been to find promising vehicle systems which would provide outstanding pro perties as water-borne finishes. The field of water-soluble polymers was broadly and systematically assessed In earlier work under this program. Several preferred routes had been selected for our synthetic studies. (See Report R-60-13, P.4-5 for the detail). On basis of our systematic assessment and current synthetic studies, acrylic terpolymers containing 5-10$ Itaconic acid have been found to be most promising. Itaconic acid terpolymers have shown solubility In aqueous ammonia at a low level (5$) of carboxyl content and convertibility on baking to essentially non-ionic imide structure. COONH4 (-CH2-C-)n I CH2 ---> (-CH2-C-)n /\ 0=c CH2 + 2H20 + NH^ COONH4 NH -- C=0 From literature information, ammonium salts of C4 diearboxyllc acids such as succinic acid form Imides in good yields (82-83$) by simple heating. (1) Ammonium and ethanolamine salts of a 50/50 styrene/ Itaconic acid were made and their aqueous solutions baked at 200F , 250F and 300F for 30 minutes. Analytical data indicated polyimide structtires were formed on baking. (Nitrogen content 4.91$ as against 6.13$ of the theoretical polyimide). Recently, it was found that combination of an organic diamine with ammonium salts of itaconic acid terpolymers gave cross-linked polyimide structures on baking. The resulting films were Insoluble In organic solvents (methyl ethyl ketone and dimethyl formamide) and showed a high degree of water resistance. Itaconic acid copolymers and terpolymers of acrylonitrile, methyl methacrylate, ethyl and butyl acrylate and stryene have been used in the polymer backbone. Organic diamines such as ethylenediamine, hexamethylenedlamine, 2,4-diaminotoluene and bis(4-aminocyclohexyl)methane have been used for the cross-linking. DUP0300091 97 -5- COONH^ 2(-CHg-C-)n i CHg i COONH|| ---------------------* + NH2(CH2)6NH2 ("CH2"C-)n CH0 C=0 ; *I CO- N ! (CHg)6 CO - N + 4h 2o + 4NHg CEq 0*0 (-CHg-C-)n Preparation of Itaconic Acid Copolymer and Terpolymers (a typical example). Styrene/ltaconic acid copolymer (D-95087-1 NB 710? p. 109). Fifty grams of styrene, 50 g.of itaconic acid, 100 g. of dioxane and 1 g. of benzoyl peroxide were charged into a popbottle. The bottle was flushed with nitrogen, capped, and heated at 85C for 16 hours in a tumbling bath. The conversion of monomers to copolymer was quantitative as indicated by solids determination. The preparation of other itaconic acid copolymers and terpolymers is listed in Table I. From literature information, sulfonium compounds have been shown to be water-soluble and to convert to water-insoluble compounds on standing or mild heating (References 4 and 5). DUP030009198 a. RCH2CH2S(CHo )2 - 6- - f RCH=CHg + (CHo)pS + H20 OH -----( ^RCHgCHgSCH^ + CH^OH In 1956, E. L. Buhle found that dodecyl methyl phenyl sulfonium acetate, a water-soluble cationic dispersant, converted to water-insoluble product under "air-dry" conditions, (2 and 3). A phase of our scouting program has been to utilize this principle in the field of water-soluble, room temperature convertible sulfonium polymers. Anionic trlmethyl sulfonium polymers have been made by neutralizing MMA/BA/IA terpolymers with trimethyl sulfonium hydroxide. c h 2c o o h 1 (CH2-C-)n I + 2(CHo)3 S+OH- COOH c h 2c o o - s +(c h 3)3 1 >. (-CHg C--)n !+ C00" S(GH3)3 Anionic Trimethylsulfonium Polymers These polymers have been shown to convert to corresponding methyl ester on low bakes. However, room temperature conversion reaction were slow and did not yield water-insensitive films. Cationic sulfonium polymers derived from poly-2-ethylthioethyl methacrylate have also been made. CH3 CH- (c h 2-c -)n H CH3X COOCH^CHg-S-Cg^ ( -- CH -C-- ) 2 t n + X" COOCHgCHg-S-R CHo X * Methyl Sulfate, Iodide, acetate, etc. Cationic Sulfonium Polymers The acetate salt of the above polymer appears to show promise as the room temperature convertible system. Prom the literature Information (Reference 6), dimethyl sulfide has been shown to react with beta-propiolactone to give dimethyl-beta-propiothetin salts In good yield. DUP030009199 -7+ HC1----- (CH3)2 -I" SCIT CHgCHgCOOH Attempts to prepare propiothetin polymers by reacting poly-2ethythioethyl methacrylate with beta-propiolactone have been unsuccessful. CHo I (OK - c - ) ^I COOCHgCHg- S-R 0H5.-CH,, + if 0 -- C=*0 oh3 (c h 2- o - )n + COOCHgCHg-S-R CHgCHgCOO" DUP030009200 -8- EVALUATION RESULT OP ITACONIC ACID TERPOLYMERS CROSS-LINKED WITH DIAMINES A. Typical Example Five grams of a 40/50/10 S/EA/lA terpolymer (D-95123 as a 50fo solution in butyl carbitol, H-648) was neutralized, with 5 ml cone, ammonium hydroxide and diluted with 20 ml distilled water to give a clear and homogeneous solution. To this solution, 0.223 g. of hexamethylenedlamine (m.p. 39-42C, chemically pure grade, supplied by Matheson, Coleman & Bell Lot #6115 HX-315) was added. The amount of hexamethylene diamine was calculated on the basis of one mole of diamine for two moles of itaconic acid in the terpolymer. The ammonium salt of Itaconic terpolymer and the diamine solution was doctor bladed over four Bonderite steel panels and then baked at 300F for 30 minutes. Film properties such as adhesion (TM-37) were excellent; impact (TM-386-A) was excellent; humidity (TM-214) was 10 and solvent resistances to MEK and xylene were very good. Other aqueous ammonia soluble itaconic acid terpolymers Including 50/40/10 MMA/EA/lA, 52.8/42.2/5.0 MMA/BA/IA and 59/31/10 AN/BA/IA have been used as the polymer backbones. Other diamines including ethylenediamine, 2,4-diaminotoluene and bis(4-aminocyclohexyl)methane have been used as the cross-linking agent. However, the hexamethylenedlamine cross-linked films gave the best flexibility-hardness balance. PREPARATION OF EXPERIMENTAL AUTOMOTIVE SHEET PRIMER (W-20925 NB 7297 p, 44) Vehicle Used 400 g. 40 ml 7.6 g. 80 ml 40/50/10 S/EA/IA in 50# butyl cellosolve distilled water hexamethylenedlamine (MC & B HX-315) in distilled water (W-20908B) Pigment Used 11.1 g. 10.8 g. 73.4 g. 147.2 g. M-50 Lead Sllicochromate (supplied by National Lead Co.) W-222 Molacco Black W-I38 Micronized Talc W-1008 Aluminum Silicate DUP030009201 - 9- Thinner 200 ml Distilled water The above Ingredients were ground In a gallon porcelain mill filled with pebbles. The primer had a solids of 30.4$ by weight and a viscosity of 16 seconds (#15 Parlin cup) or 3 minutes 3 seconds (#3 Zahn cup). The fineness of the primer was less than 0.5 mil. Evaluation results of the above experimental primer are listed in Table II. PREPARATION OP EXPERIMENTAL APPLIANCE ENAMEL (-20938 NB 7297 P. 65) Vehicle Used 800 g. 80 ml 320 g. 15.2 g. 160 g. 40/50/10 S/EA/lA as a 50$ solution in butyl cellosolve (W-20908B) cone, ammonium hydroxide Distilled water Hexamethylenediamlne (MP 39-41C) supplied by Mabheson, Coleman & Bell Lot No. HX-315) in distilled water Pigment Used 400 g. -43 titanium dioxide The vehicle and the pigment were ground in a "47 Process" (2 passes). Additional amount of water (100 g.) was added during and after the grinding to adjust to the desired viscosity. The fineness of the enamel was 0.5 mil and the yield was 1450 g. Solids of the enamel = 43.5$. Pigment/binder ratio =* 100/100. Note: The amount of hexamethylenediamlne was calculated on the basis of 85$ of the theory. Evaluation of the Experimental Appliance Enamel. The experimental appliance enamel (-20938) was evaluated briefly. This enamel was doctor bladed over DUP030009202 10 Bonderite 1000 panels and baked at 300F for 30 minutes. The resulting films had a hardness of 22.8 (Knoop), a gloss of 88.il- (85). These films have shown good resistance to xylene and methyl ethyl kfetone and good resistance to humidity (100# RH at 120F for 2 weeks). SCALE UP OP STYRENE/ETHYL ACRYLATE/lTACONIC ACID TERPOLYMERS (W-20941 NB 7297 p. 70) To a 3-liter, 3-neck flask equipped with stirrer, thermometer, nitrogen lead, reflux condenser and dropping funnel, and heated by an electric heating mantle, was charged 128 g. of butyl cellosolve (H-224). The charge was heated to reflux (130-142C) under a nitrogen blanket and the mixed monomers-initiator-solvent charge was added in four equal portions at one hour intervals while reflux was maintained. Monomers-Initiator-Solvent Charge 700 g, Sytrene (rubber grade H-710) 200 g. EA (Rohm & Haas #1669) 100 g. IA (Eastman #2690) 538 g. H-224 Butyl Cellosolve 20 g. Di-tert-butyl Peroxide (H-640) The polymerization was somewhat exothermic. This was controlled by proper heating Input and by the refluxing of the solvent. After the addition of the monomer charge, the heating was continued for an additional hour. The temperature of the reaction was maintained between 130-142C throughout the polymerization. At this point, the polymerization was essentially completed. The solids were 59.7$ which was calculated to be 99.4$ conversion. After cooling the polymer solution, it was neutralized with 200 ml cone, ammonium hydroxide and 1134 ml of distilled water to give a clear and viscous solution. The solids of this aqueous solution was 33.7$ and the yield was nearly quantitative. DUP030009203 11 TRIMETHYLSUU'Q'Ja'dM SALT OF 50/50 STYRENE/lTACONIC ACID COPOLYMER Twenty grams of 50/50 styrene/itaconic acid copolymer In dioxan was neutralized with 49 ml of 1.57N trimethylsulfonium hydroxide (DS-44731, supplied by Crown Zellerbach Corp.) and diluted further with 31 g. distilled water. The resulting solution was clear and homogeneous. This polymer solution was doctor-bladed on eight 5" x 7" glass panels. Eight panels were divided into four duplicate sets. One was air-dried at the room temperature for 48 hrs. Other three sets were baked at 200F, 250P and 300F for 30 minutes, respectively. These films (except the air-dried one which was tacky after 48 hours at the room temperature) were scraped from the glass panels and submitted for analysis. The results of the analysis are shown in Table. Analysis of Baked Films of Trimethyl Sulfonium Salts of 50/50 Styrene/Itaconic Acid Copolymer. BAKING TEMPERATURE SULFUR CONTENT ACID NUMBER SAPONIFICATION NO. 200F 250 F 300F 1.17$ 0 0 1.9-9 27.3 - 232.8 193.0 - ,v Theoretical 15.5# 0 390 PREPARATION OF 2-ETHYLTHIOETHYL METHACRYLATE (D-95126, NB 7107 P. 155) Methyl Methacrylate Monomer H-428 500 g. 2-Ethylthioethanol (Pennsalt DS-44791) 106 g. Hydroquinine (Fisher Chemical Lot #H-329) 5 g. Sodium Methoxide (Matheson, Coleman & Bell 59^3) 2 g. The above materials were charged into a 2-liter, 3-neck flask equipped with stirrer, continuous water separator-condenser and thermometer. The reaction mixture was heated to reflux (92-110C) for 4 hours. An azeotrope consisting of methanol and methyl methacrylate was distilled off. DUP030009204 12 The temperature of the distilling head was kept between 64-67C. The reflux was continued for about one more hour after which time the reaction was nearly completed. The excess methyl methacrylate was stripped off under an aspirator vacuum and the product was distilled over at 59-68C (0.4-0.6 mm). The yield of the crude product was 150 g. (78.5$ of the theoretical). This product was purified further by redistillation (b.p.59-62C at 0.4-0.6 mm). Yield of the pure product was 60 g. $C $H $S Anal, calc'd. for C8Hi2|02S: 55.1 8.1 18.4 Found: 55.0 8.52 17.93 PREPARATION OF POLY-2-ETHYLTHIOETHYL METHACRYLATE j Twenty grams of 2-ethythioethyl methacrylate monomer (D-95126) 20 g. of acetonitrile and 0.5 g. azo-bls-lsobutyronltrile (QY-602) were charged into a pop-bottle. The bottle was then flushed with nitrogen and tightly capped using a thin "Mylar"* film to prevent any contamination from the cork. The polymeriza tion was carried out in a tumbling bath for 16 hours. The temperature of the polymerization bath was maintained at 85C + 0.5C. The conversion of monomer to polymer was 98.4$ indicated by a solids determination. PREPARATION OF WATER-SOLUBLE SULFONIUM POLYMERS DERIVED FROM POLY- 2 -ETHYLTHIOETHYL METHACRYLATE A. With Methyl Iodide Ten grams of poly-2-ethylthioethyl methacrylate solution (0.0287 equivalent) In acetonitrile (D-95133) was thoroughly mixed with 10.0 g. methyl Iodide (0.071 equiv.) in a 250 ml flask. The mixture was kept at the room temperature in a dark place for 16 hours. To the reaction mixture there was added 200 ml of anhydrous ethyl ether. The polymeric product that precipitated was decanted and washed twice with 200 mil portions of ether. The resulting polymer was dissolved In 27 ml distilled water to give a clear and somewhat viscous solution indicating -Registered Du Pont Trademark DUP030009205 - 13 - that the sulfonlum polymer had formed. B. With Methyl Sulfate Ten grams of poly-2-ethylthioethyl methacrylate solution (0.0287 equivalent) in acetonitrile (D-95133) was thoroughly mixed with 9-0 g. of dimethyl sulfate (0.072 equiv.) in a 250 ml flask. The mixture was kept at the room temperature overnight. To the reaction mixture, 200 ml of anhydrous ethyl ether was added to precipitate the polymeric product. The product was decanted from the liquid phase and washed twice with 200 ml portions of ether. The resulting polymer was dissolved in 26 ml of distilled water to give a clear and viscous solution. ' C. Convertible Sulfonlum Acetate Polymer The sulfonlum iodide salt solution of poly-2-etbylthioethyl methacrylate described under A, was treated with a lead acetate solution containing 5.45 g. (0.0143 equiv.) of PbACo-SHgOand 20 ml of distilled water. The lead iodide precipitate was filtered off. The clear polymer solution was flowed out on a 5" x 7" glass plate. After overnight drying at room temperature, the film was no longer water-soluble. ATTEMPTED REACTION OP POLY-2-ETHYLTHIOETHYL METHACRYLATE WITH BETA-PROPIOLACTONE. A. Ten grams of a 50$ solution of poly-2-ethylthioethyl methacrylate in nitromethane and 10 grams of beta-propiolactone were charged into a 3-neck, 250 ml flask equipped with a gas Inlet tube, a magnetic stirrer, a thermometer and a reflux condenser. A stream of anhydrous hydrogen chloride was bulbed through the reaction mixture at a temperature of 25-3GC for one hour. The mixture was kept at room temperature for 54 hours. To this mixture, 200 ml of anhydrous ethyl ether was added to precipitate the polymer. The precipitate was washed by de cantation twice with 20 ml portions of ether. The resulting polymer was not soluble in water indicating that poly-2-ethylthioethyl methacrylate did not react with beta-propiolactone. JCF/McD Cj/2076i:' DUP030009206 - 14 LITERATURE REFERENCES; (1) Suecimide was made in 8356 yield by heating ammonium succinate. Org. Syntheses Col. Vol. II, page 562. (2) Convertible Dispersing Agents for Finishes. Research Reports 1361, 1404, R-56-16, R-56-49 and R-57-35. (3) Convertible Sulfonium Dispersants. R-57-65. (4) Thermal Decomposition of Sulfonium Hydroxides. J. Chem. Soc,, 533 (1933). (5) Decomposition of Triethylpulfonium Bromide. Trans. Faraday Soc., 23 605 (1927). (6) Dimethyl-beta-propiothetin Hydrochloride was made by reacting dimethyl sulfide with beta-propiolactone. J. Am. Chem. Soc., 73, 2355 (1951). DUP030009207 - 15 - TABLE I PREPARATION OF 1TACONIC ACID TERPOLYMERS Polymerization Temperature 83 C., Time 16 Hours Code Compositions w-20903-I 59/31/10 AN/BA/IA * Molecular Solubility n b 7297 Conversion Weight(1) in NHiiOH (2) page 89.8 - Soluble 6 W-20903-II 33/57/10 a n /b a /ia 91.8 - Soluble 6 W-20905-l 90/10 MMA/IA W-20905-2 90/10 EA/IA W-209O8-A 50A0/10 MMA/EA/IA 100 97.6 100 72,000 65,000 72,000 Soluble Soluble Soluble 9 9 18 W-209O8-B 50/40/10 EA/S/IA W-20908-C 50/40/10 MMA/EA/MA 99.6 100 38,000 Soluble - Insoluble 18 18 W-20908-D 50/40/10 MMA/EA/lA 96.8 - Insoluble 18 W-20912-A 56/29/15 AN/BA/IA W-20912-B 58/30/12 a n /b a /ia -20916-A 59/31/10 a n /b a /ia 100 100 59 ~ Soluble - Soluble - Soluble 24 24 28 -20920 40/50/5/5 s /e a /ia /a a 100 - Soluble 39 w-2093 9i 60/32/8 S/EA/IA 96.4 38,000 Partially Soluble 66 DUP030009208 - 16 Table I Cont'd. Code 1Compositions W-20939-III 70/22/8 S/EA/IA W-20939-V 80/12/8 S/EA/IA Molecular Solubility NB7297 $ Conversion Weight(l) In NHH0H(2) Page 95.8 94.4 - Partially 66 Soluble - 1! W-20940-I 60/30/10 S/EA/IA 95.4 37*000 Soluble 67 W-20940-III 70/20/10 S/EA/IA 94.6 - Soluble 67 W-209^0-V 80/10/10 S/EA/IA 94.2 - Soluble 67 -20942 42/50/8 MMA/EA/IA 98.8 61,000 Soluble 72 w-20943 42/50/8 (3) MMA/EA/IA 98.8 - Soluble 72 (1) Determined from relative viscosity in ethylenedlcbloride and the viscosity - molecular weight curve for polymethyl methacrylate. (2) Soluble of polymer was determined by dissolving 1 g. polymer in 10 g. of 10$ NH4OH. (3) Polymer made in 70$ butyl cellosolve. DUP030009209 TABLE X I EVALUATION OF AUTOMOTIVE SHEET METAL PRIMER (NOTEBOOK 7297, p . 6 0 ~ 6 l) CQ s EU Eh <C H in vo y5 P-l rl CO CO in ro-l or--I or-H d\ in in in 0\ Ch CT\ CT\ in o\ o\ o\ o As B s o H CO CM* 00 00 t- c- m m# o o in in in in o On veH CQ lO N O co in ro ,h in in in vo g 8; s coo x icCnvMi O oini in ccoo = s3r I CD rl rd 8* oon mo oco o cm X XX X oo in cm oin oo co co on -s- in aCoM\ CMi Ss 8 VO rIl 3 rl W (O 4 t-- r-l oco x mo CM in CcdT--\ ccmo- 8 mo oCO CoO oCM x XXX ocoo mcc mo ciono o-ost in 8 oo\ e S vo 8 5* in VO t*- CO 6U* H CD 55 +CD tL 4J rl JGCO Sx Se>j gj JpB W -I! g> P3 O H O' S rj* 1II -=* un *&- d$oopo ' in.=j* 3SSS P ao DUP030009210