Document rpzNkQZQDBrynobbOG8219GEe

TECHNICAL BULLETIN PLASTICIZERS FOR HARD-TO-PLASTICIZE RESINS TECHNICAL BULLETIN 0/PL-332A J Monsanto ri 0212633 TOWOLDMONOQ25417 PLASTICIZERS FOR HARD-TO-PLASTICIZE RESINS TECHNICAL BULLETIN 0/PL-332A 021263A "Nothlnj contilned herein It to be construed is recommendation to use iny product in conflict With tny pilent. MONSANTO MAKIS NO WARRANTIES AS TO THE FITNESS OR MERCHANT ABILITY OF ANY PRODUCTS REFERRED TO, no luerentee of tltlsliclory results Irom relience upon conUined informttion or recommendations, end dltctilms ell HottUly lor my reiulfinj loss or demije.'" Organic Chemicals Division/800 N. Lindbergh Blvd./St. Louis, Missouri 63166 1 TOWOLDMONOQ25418  Contents Introduction................................................................3 Guide To Monsanto Plasticizers For Hard-To-Plasticize Resins................................4 Acrylic Resins............................................................6 Epoxy Resins................................................................8 Polyester Resins..........................................................TO Polyamide Resins......................................................12 Phenolic Resins..........................................................14 Melamine Resins......................................................16 Synthetic Rubbers......................................................17 Polyvinylidene Chloride .............................................. 23 Polyvinylpyrrolidone..................................................25 Protein Resins..........................................................27 Asphalt and Shellac..................................................30 Plasticizer Council......................................................31 Technical Bulletins on Monsanto Plasticizers ... 32 ^ 2 TOWOLDMONOQ25419 Introduction Hundreds of plasticizers are commercially available to plasticize and modify vinyl, cellulosic, and other easily-plasticized resins. Yet there are numerous unfilled needs for suitable plasticizers for many other resins, especially some of the thermosetting resins, that are more difficult to plasticize satisfactorily. Many formulators require just the right plasticizer to improve the performance of a particular resin in an existing application, to make it suitable for a new application, or to improve its economics to expand its market. Often the best solution to these difficult and demanding plasticizing problems already exists among Monsanto's more-than-eighty plasti cizers. Monsanto's Plasticizer Council, with its years of cumulative experience with virtually every kind of commercial resin, offers un matched competence and know-how with which to seek and find answers to the toughest plasticizing requirements. This bulletin has been prepared to give you some idea of the breadth and versatility of Monsanto's knowledge, experience, and plasticizers. We hope that you will consult it often for preliminary information about resins that require a plasticizer or that could be improved by the use of a better plasticizer. For more detailed information, we will gladly send you Monsanto technical bulletins on indicated plasticizers or on the general application area. Of course your specific inquiry to the Plasticizer Council, directed either to the nearest Monsanto Service Center or to the Plasticizer Sales Department in St. Louis, will receive prompt, expert attention. 3 TOWOLDMONOQ25420 i Guide to Monsanto Plasticizers for Hard-To-Plastic ize Resins Plasticizer Acrylic Epoxy Poly ester Polyamide nylon dimer acidbased Phenolic Mela mine Chlor inated rubber Styrene Buta diene Neo prene 1 1: dibutyl XX X dicyclohexyl X diethyl X diisodecyl dimethyl X X X dioctyl X diphenyl Santicizer* 160 X X Santicizer 213 X X X _______ [ ., X XX diisodecyl dioctyl Tricresyl XX X Triphenyl Santicizer 140 X X Santicizer 141 XX XX i1 4X XX X I X X --twfiji J X X1 Santicizer E-15 Santicizer B-16 Santicizer M*17 X X X X XX -- Santicizer 1-H Santicizer 3 Santicizer 8 Santicizer 9 Santolite* MHP Santolite MS-80% Other HB-40* Mod-Epox* Triphenyl Phosphite Montar* Aroclor* Santicizer 409 Santicizer 411 X X X X X 1221 1254 1248 1260 5460 1262 1260 4465 5460 X X X X X X X X XX XX X X X X 1268 5460 1262 'SinUelnr Santo*!*, HB-40, Mod-1 pen, Montir, end Aroclor iro Monunto Compony trademark*, raclstarad in the U. S. Pitoni Offiea. X X X X -- X 1268 5460 -- TOWOLDMONOQ25421 X-marks denote the plasticizers mentioned in this bulletin as being most generally useful in the indicated resin. Since other plasticizers may be used for special applications, and since Monsanto is constantly adding to its vast fund of knowledge about plasticizer/resin systems, it is always a good idea to ask Monsanto's Plasticizer Council for advice on difficult or unusual plasticizer-formulation problems. Poly butene Nitrile rubber Poly sulfide Sili cone rubber Crepe rubber Vlnylpyrrolldone Polyvinyl- Vinyl idene Homo Acetate chloride polymer Copolymer Casein Zein Soya Ally! starch Shellac Asphalt XX X X X XX X X X XX XX X X X X XX X X X X A w X X X X X X XX XX XX X X X XX X X XX X X X X X X XX X X XX X XX X X XX XX X XX XX X X X 1232 X 1262 5460 X XX X X 5460 X X ' ' " TOWOLDMONOQ25422 0 Acrylic Resins Polymers of acrylic and methacrylic acids and esters are noted for their clarity and outstanding light and weather resistance. They are widely used in extrusions, sheet, injection moldings, castings, fibers, and adhesives. A major expanding use of acrylic resins is in solution coatings, where they impart exceptional durability, light-fastness, hardness, and high gloss upon polishing. Since acrylic and acrylic-modified lacquers have performed so exceptionally under the tough conditions imposed by automobiles and aircraft, they are becoming increasingly accepted in both air-dry and baking lacquers for other metal-finishing applications, including appliances, machinery, motors, furniture, and shipping drums. Poor adhesivity of acrylics to the substrate is a major deficiency that can be overcome only by the use of external plasticizers. Suitable plasticizers, therefore, must impart adhesion and should also improve flexibility, durability, and gloss; reduce sensitivity to moisture and high humidity; improve economics by extending the more costly resin; and have the least effect on the desirable properties of the acrylic resin. Santicizer 160 has become the standard plasticizer for polymethyl methacrylate because it offers the best balance of desirable properties and has the best cost/performance characteristics. Acrylic coatings plasticized with Santicizer 160 offer excellent adhesion, gloss, humidity compatibility, levelling, flexibility, light stability, and cold-check resistance. Dicyclohexyl phthalate is sometimes used with Santicizer 160 to achieve harder lacquers and to improve moisture resistance. Santicizer 409, a polymeric plasticizer, is incompatible with acrylic resins, but when used with Santicizer 160 it reduces the plasticizer loss by vola tilization. In Monsanto's continuing research and development programs to produce ever-better plasticizers, several promising candidates are equal to or better than Santicizer 160.in most important qualities yet are much less volatile. Performance characteristics of various plasticizers with acrylic resins are compared with those of Santicizer 160 as the standard plasticizer in Table I. (Plus signs indicate that the plasticizer performs better than Santicizer 160 in the indicated property; minus signs denote poorer performance.) # on***' i f 6\ I TOWOLDMONOQ25423 TABLE I -- Plasticizer Performance in Acrylic Resin PlMliolur NONE Santicizer 160 Dimethyl Phthalete Diethyl Phthalate Dibutyl Phthalate Dioctyl Phthalate Diisodecyl Phthalate Santicizer B-16 Dicyclohexyl Phthalate DCHP/Santicizer 160 (2/1) DCHP/Santicizer 160 (1/2) Tricresyl Phosphate Santicizer 140 Santicizer 141 Santicizer 409 Santicizer 409/Santicizer 160 (2/1) Santicizer 409/Santicizer 160 (1/1) Santicizer 409/Santicizer 160 (1/2) Solvency" Standard + + 4equivalent -- -- equivalent - equivalent Volatility* (100C, 23 hr.) Plast Lost (%) 44.0 (Std) 43.8 41.7 46.3 41.5 4.5 49.7 29.0 30.0 12.4 31.0 45.2 Repalrab!lltyc (Solvent Craze) -- Standard + -_ equivalent ++ Humidity* Stability equivalent Standard Light" Stability (gloss) 84 78 (Std) - -- - -- - 67 80 80 67 75 __ 27.5 _- 36.3 slight neg. slight neg. equivalent equivalent 71 a) Solvency compared to that of Santicizer 160 in one or more of three ways: film solvation, gel tempera ture of plasticizer-resin mixture or of piasticized-iacquer system, and viscosity of plasticized lacquers. b) Values for volatility may also include solvent loss because of poor solvent release. e) Comparison of observed checking after either 8-minute immersion of plasticized-lacquer on tinplate into toluene or application of second lacquer coat over dried coat, or both. d) Plasticized lacquer on primed-steel panels immersed in distilled water at 40C for 100 hours, then panels rated according to ASTM test D-714. e) Plasticized-lacquer films on glass panels exposed in Weather-OmeUr* for 125 hours, then gloss measured (highest values are best). Tndimirk o( Mill tUctrk Dvlc*t Co. 021?b<*0 1 TOWOLDMONOQ25424 Epoxy Resins Epoxy resins generally are chemically resistant, flexible, tough, and adhesive. Available as solids, liquids, or solutions, they are useful in surface coatings, including chemical-resistant coatings, maintenance coatings, baking finishes, and laminates; in adhesives; and in encapsula tion, potting, lamination, and casting compounds. Plasticizers are not ordinarily used in epoxy resins when maximum performance is desired. Because of their high cost, however, epoxy resins are often highly filled. Diluents are also often added to reduce the viscosity of liquid epoxy resins, to make them easier to handle. Performance evaluations of several Monsanto plasticizers and reactive diluents for epoxy resins are tabulated in Table II. APPLICATIONS Surface Coatings In surface coatings, the use of Aroclor 1264, Aroclor 1260, or Aroclor 1262 imparts excellent chemical resistance, especially to acids and alkalies; flame retardance; and economy. Aroclor plasticizers should not be used where resistance to solvents is desired, since they are true plasticizers and do not combine chemically with the epoxy resin. Adhesives In adhesives, including polyamide-epoxy resin combinations, evaluation of Mod-Epox, Aroclor 1254, and Santicizer 8 is recommended. Encapsulation, Potting, Lamination, and Casting For lower viscosity to aid processing, at lower costs, but with minimum change in physical properties, Mod-Epox and Santicizer 8 are suggested for use in epoxy encapsulating, potting, laminating, and casting com pounds. These reactive diluents react chemically with the resin so that the final properties are very similar to those of the unmodified resin. Where additional softness or flexibility are desired, Santicizer 141 especially, Santicizer M-17, Santicizer B-16, Aroclor 1221, Santicizer E-15, tricresyl phosphate, Santicizer 140, or Aroclor 1248 may be used. On aging, some or all of this flexibility may be lost, depending on the temperature of exposure. MONSANTO PLASTICIZERS Aroclor Plasticizers The Aroclor plasticizers are the most compatible of all the nonreactive plasticizers evaluated. Like epoxy resins, they impart excellent chemical and oxidation resistance and improved adhesivity. Flammability and cost -- two major limitations of epoxy resins -- are diminished through the use of Aroclor compounds: nonbuming com- 0 1 oil***1 TOWOLDMONOQ25425 TABLE II -- Performance of Monsanto Plasticizers and Reactive Diluents in Epoxy Resins Viscosity' Physical Properties After Cure (0.6 hr 100C) Plasticizer*1 None (control) Dibutyl Phthalate Santicizer E-15 Santicizer M-17 Santicizer B-16 Tricresyl phosphate Santicizer 140 Santicizer 141 Aroclor 1248 Aroclor 1221 Mod-Epox Santicizer 8 Before Adding Curing Agent (CP) 12,800"* 1550 3050 3150 2300 3750 2850 1500 7700 1650 1650 7600 After Adding Curing Agent (op) 7900 1300 2100 2450 2000 3000 2200 1400 4300 1200 1250 3100 Izod impact Resistance 0.2 -- -- -- -- -- -- -- 0.6 -- 0.8-0.9 0.2 Clarity; light reflected {%) 3.0 3.5 2,5 3.0 4.5 3.5 3.5 4.0 3.0 3.0 4.0 3.0 Hardness, Shore "D" (10 sec) 78 10 10 6 7 15 22 5 40 8 84 84 Physical Properties After Heat Aging (24 hours Hardness, Shore "D" (10 sec) 86 78 80 85 85 86 79 82 88 81 88 88 Weight Change (%) -0.012 -0.734 0.119 -0.131 -0.013 -0.222 -0.284 -0.425 -0.682 -2.118 0.134 -0.007 o) Formulation Ingredients Parts Epoxy Resin Plasticizer Tetraethylenepentamine 100 25 8 6) All are compatible in the liquid resin and in the cured resin; both at room temperature and after 0.5 hour at 100C c) Brookfield LVF #4 spindle; 60 rpm unless otherwise specified d) 80 rpm positions are made by the use of an Aroclor compound (15 PHR) and antimony oxide (5 PHR). About one-fourth the cost of epoxy resins, Aroclor plasticizers permit significant cost reduction. The use of the liquid Aroclor plasticizers (1221 and 1248) in aliphatic amine-cured epoxies also improves flexural strength and compressiveyield strength, has little effect on tensile strength, and only slightly lowers heat-distortion temperature and ultimate compressive strength. They are commonly used in solventless coatings. Solid Aroclor compounds (1262 and 5460) greatly improve compressive strength, compressive-yield strength, flexural strength, and tensile strength; although they slightly lower the heat distortion temperature. They are used, sometimes in combination with liquid Aroclor plasti cizers, in solvent-containing coatings. Extension of epoxy-resin adhesives with Aroclor compounds greatly reduces the formulation cost and has minimum effect on the bonding characteristics of the adhesive. 021?64 2 9 TOWOLDMONOQ25426 Mod-Epox Ordinary reactive diluents reduce the viscosity of epoxy resins and thereby improve handling characteristics and permit the use of higher filler contents. Since they react with the curing agent and cost more than the epoxy resins, however, they generally tend to increase the cost of the formulation. Mod-Epox, by contrast, not only reduces the viscosity of liquid epoxy resins by as much as 75 per cent but also speeds cure, reduces curingagent requirements by about one-third, improves bond strength of adhesives, and maintains hardness and other chemical and physical properties. Since it costs much less than any epoxy resin and any other reactive epoxy modifier, and since it lowers the curing-agent require ment, the incorporation of Mod-Epox generally lowers the formulation cost greatly. Furthermore, Mod-Epox is not a skin irritant like many other reactive diluents. Santicizer 8 Santicizer 8 is another reactive diluent that effectively lowers the viscosity of epoxy resins and decreases the curing-agent requirement, without detriment to physical properties except for heat-distortion temperature. A major, new, unique benefit of the use of Santicizer 8 is that the polyamine curing agent can be diluted in it for easier handling and more accurate metering. The use of solutions of curing agent in Santicizer 8 should help to eliminate measuring errors and thereby reduce the fre quency of overcured or undercured batches of epoxy resins. Polyester Resins Fiberglass-reinforced polyester resins are widely used for the manu facture of industrial and consumer products because of their high strength-to-weight ratio, ease of fabrication of large and complex forms, and chemical resistance. Molded articles, including buttons, are also made of polyester resins. Although polyester resins are most often not plasticized, modification of their physical properties by plasticizers is desirable for some applica tions. Some of these modifications, and the appropriate Monsanto plasticizers that best impart them, are as follows: Flame-retardance Flexibility Resilience Moldability, gloss, and moisture resistance Faster processing, clarity Initiator carriers (for easier, safer handling) Aroclor 1260, 4465, and 5460 Santicizer 160, Aroclor 1260, 4465, and 5460 Santicizer 160 Santicizer 9 Triphenyl phosphite Dimethyl phthalate, Dibutyl phthalate, Tricresyl phosphate, and Santicizer 160 0 10 TOWOLDMONOQ25427 Polyester curing initiators are diluted with dimethyl phthatate, dibutyl phthatate, tricresyl phosphate, or Santicizer 160 for easier, safer handling. In polyester coatings, Aroclor plasticizers Impart flame retardance. MONSANTO PLASTICIZERS Aroclor Plasticizers The highly chlorinated, low-volatile, solid Aroclor plasticizers, such as Aroclor 1260, 4465, and 5460, are very effective and economical flame retardants for polyester resins, and they can increase the flexibility of the resin. Flame-retardant combinations of equal quantities of an Aroclor compound and antimony oxide act synergistically; the Aroclor compound imparts self-extinguishing properties to the resin, and antimony oxide reduces after-glow. The use of an Aroclor compound to impart flame retardance to a poly ester resin offers the added advantage of eliminating the need for a higher-cost flexibilizing polyester, since the Aroclor compound increases the flexibility of the naturally brittle resin. At 10-per cent concentration (enough, with an equal amount of antimony oxide, to make the polyester resin self extinguishing) these three Aroclor compounds have from slightly less to slightly more effect on flexural strength and on flexural modulus of a reinforced polyester than a flexibilizing polyester does. At 20-per cent concentrations, each of these Aroclor compounds increases the impact strength of the polyester resin, whereas the flexibilizing polyester decreases it. Santicizer 160 The use of Santicizer 160 as an external plasticizer in polyester resins increases flexibility and resilience (U. S. Patent No. 2,757,158, J. R. Darby and A. R. Hempel, assigned to Monsanto Company). Cast sheet consisting of from 15 to 50 parts Santicizer 160 per 100 parts unsaturated polyester resin and 37.5 parts styrene is hard, tough, and resilient; whereas similar sheet without Santicizer 160 is hard and tough, but very brittle. 021264* 11 TOWOLDMONOQ25428 Santicizer 9 Santicizer 9 improves processability of polyester molding compounds and also imparts gloss and moisture resistance to molded products, such as buttons. Catalyst/Clarifier -- Triphenyl Phosphite In the presence of a small amount of Monsanto triphenyl phosphite, the processing time of polyester and alkyd resins is shortened--and lighter, clearer products are obtained. For example the processing time for a maleic anhydride-ethylene glycol polyester resin was reduced from 95 to 80 minutes, and the final resin color was improved from APHA 20-25 to APHA 15-20 by the addition of 0.5-per cent triphenyl phosphite. Peroxide-Initiator Carriers Peroxide initiators ("catalysts") used in polyester-resin processing are more easily handled if diluted and desensitized by compatible plasticizers such as dimethyl phthalate, dibutyl phthalate, tricresyl phosphate, and Santicizer 160. Polyamide Resins NYLON Plasticizers impart better low-temperature flexibility and improved impact resistance to nylon, increasingly important benefits since carbon black and other fillers tend to reduce these properties. Monsanto's sulfonamide plasticizers and resins--Santicizer 1-H, Santicizer 3, Santicizer 8, Santicizer 9, Santolite MHP, and Santolite MS-80%--are useful as flexibilizers and modifiers for nylon. Perform ance evaluations of five of these plasticizers are compared in the following table: TABLE III -- Evaluation of Plasticizers in Nylon* Plasticizer (25 PHR) None (control) Santicizer 1-H Santicizer 3 Santicizer 8 Santicizer 9 Santolite MHP Stiffness at 77F (psi) 35,900 11,560 10,850 12,700 9,800 5,790 Hardness (Shore "D") 67 27 34 40 58 28 Tensile Strength (psi) 5700 3080 4930 1830 3100 3960 Elong ation (%) 320 100 480 250 350 360 Water R esistance Absorbed Solubles (95) Lost (%) 2.00 1.61 0.94 1.98 1.67 1.24 0 0 0.16 1.89 1.30 1.10 a) 15 PHR *Du Font's Zytl)01 rosin TOWOLDMON0025429 Santicizer 1-H Santicizer 1-H is the most resistant plasticizer to extraction by water. Santicizer 8 Santicizer 8, the best available plasticizer for nylon, aids processing by lowering the melting point. It imparts improved toughness, flexibility, and low-temperature flexibility to nylon without affecting other resin properties. Santicizer 8 is excellent for oil-resistant nylon coatings on fabrics and paper. Santicizer 9 Santicizer 9 imparts a significant amount of flexibility to nylon with little reduction in tensile strength. Although blushing may occur at a plasticizer concentration of 25 per cent, a concentration of 20 per cent or less is usually sufficient for practical industrial uses. A patented composition* for precision casting, however, contains from 30- to 90-per cent Santicizer 9 with either nylon 6-6 or nylon 6-4. Such compo sitions, when cured, have a Brinell hardness of 8 kg/sq mm (11,400 psi) and an impact strength of 8 to 10 kg/cm (45 to 56 lb/in.). Santolite MHP As a useful extender resin, Santolite MHP materially reduces the net cost of either molding or solvent nylon compositions, without detracting from their desirable properties. OTHER POLYAMIDES Polyamide surface coatings based on dimer acids and diamines adhere exceptionally well to paper, waxed glassine, waterproof cellophane, and plastics; and they have good flexibility. These polyamide resins are also used in printing inks, overprint varnishes, paint vehicles, and hot-melt coatings and adhesives. Polyamide suspensoids give good heat-seal bonds to other surfaces and enhance the water and grease resistance of paper. Somewhat internally plasticized, polyamides need no added plasticizers for most applications. In hot-melt coatings and adhesives, though, external plasticizers are necessary. Strongly polar plasticizers, such as the sulfonamides, are extremely beneficial in these applications, since Gormin Pln| No. 1,016,59?, Oclobot 31,195), to Rogli ntlloml* dot uslne; Romult TOWOLDMONOQ25430 they impart tack, increase flexibility, improve gloss, and lower the softening and heat-sealing temperatures. Several typical polyamidebased adhesives formulations are the following: Polyamide Adhesives Starting Formulations Ingredients Versamid** 100 polyamide resin Versamid 940 polyamide resin Santicizer 8 Santicizer 9 Aroclor 1254* Dibutyl phthalate Dicaprylhexyt phthalate Staybelite*** ester #10 Paraffin (m. 130F) Candelilla wax Isopropanol Toluene LowTemperature __ 100 100 ---- ---- ---- 12 11 ---- 6-- ---- ---- ---- -- General- For Delayed- Purpose Poly Taok Hot-Melt ethylene (parts by weight) _ _ 100 100 -- 31.6 -- -- -- -- -- 5.9 29.5 29.5 100 10fc -- -- -- -- 10 4 -- -- - _ 100 16.6 -- -- 33.2 -- -- -- -- - Book binding1 _ 100 -- -- 85 -- -- -- -- -- -- - a) With a higher concentration of Santicizer 9, the tack may be delayed for several hours 6) Santicizer 8 increases the low-temperature flexibility e) U. S. Patent No. 2,612,468, assigned to the Du Pont Co. d) or Aroclor 1242, 1248, 1260, or 1262 Phenolic Resins MOLDING AND LAMINATING COMPOSITIONS Brake Bands and Clutch Faces Santicizer 9 is a valuable plasticizer and fluxing agent in the manu facture of molded phenolic-resin composition brake linings and clutch faces. By reducing the viscosity of the composition at molding and laminating temperatures, it improves flow properties. By helping to "wet" the fillers and abrasives, it helps produce a uniform mixture, which wears longer and more uniformly. Usually comprising from 5 to 10 per cent of the composition, it greatly improves flexibility. Aroclor 1268 also improves flow properties and promotes mixing and is useful in the manufacture of brake linings. Tndtmtrk of Control Mllli Coip, Titdtmirk of Ht'tulti Powdor Co, 02126*7 TOWOLDMONOQ25431 Phenolic-resin binders, plasticized with HB-40 or dibutyl phthalate, in foundry shell molds permit closer tolerances and smoother castings. Punching Laminates Several Monsanto plasticizers are often used to improve the coldpunching characteristics of phenolic-resin laminates. Tricresyl phos phate and the Aroclor compounds also impart flame retardance. Because of the sharpness of punches when tricresyl phosphate is used, at a concentration of from 5 to 10 parts per hundred parts of resin, fewer finished parts are rejected. Tricresyl phosphate also imparts some flexibility. The higher-molecular-weight Aroclor plasticizers (1262 and 6460) are often used for their flame retardancy. Electrical parts molded of phenolic-impregnated and laminated paper often need added flexibility for cold or hot punching. Both Santicizer 160 and dibutyl phthalate have good electrical properties, and at concentrations of from 5 to 10 PHR, they impart suitable punching and flexing properties. Santicizer 8 also imparts some flexibility, in addition to improving the cold-punching properties of phenolic laminates. HB-40 is also useful in electrical punching laminates. Composition Wallboard As a mixing aid, Santicizer 9 is invaluable in promoting uniformity of phenolic composition wallboard. 02126*8 TOWOLDMONOQ25432 ADHESIVES Phenolic clutch- and brake-lining adhesives, containing Santicizer 9 at a concentration of about 30 PHR, have potential applications. In various phenolic hot-melt adhesives, Santicizer 9 improves adhesion and flow of the resin. SURFACE COATINGS Phenolic surface coatings are most widely used in marine and masonry applications. In one phenolic marine varnish that performed well in a 14-month Florida weather-exposure test, Aroclor 1268 imparts a velvety finish. Santicizer 9 aids in mixing and in the achievement of uniformity in phenolic surface coatings. PRINTING INKS In phenolic resin-based inks, Santicizer 8 improves toughness and durability, and Santicizer 9 improves flexibility and printability. Melamine Resins LAMINATES In melamine laminates, Santicizer 9 improves flow characteristics, imparts greater solution stability, and permits drying to lower moisture content. Santicizer 9 produces higher-gloss finishes in baking or curing operations by improving flowout and by minimizing pigment dis coloration. Santicizer 9 also increases impact strength and abrasion resistance and improves bufTability of the finished coating or laminate. HIGH-IMPACT MOLDING COMPOUNDS Santicizer 9 improves dimensional stability and reduces warpage, the two major problems of high-impact melamine molding compounds. 1 > i T V In melamine laminates, Santicizer 9 produces higher-gloss finishes, improves buffability, and increases impact strength and abrasion resistance. 0 02126*9 TOWOLDMONOQ25433 It reduces shrinkage by permitting the molding powder to be made with a lower volatile content, and it reduces warpage by preventing develop ment of some of the internal stresses. INTUMESCENT, FIRE-RETARDANT COATINGS A combination of either Santicizer 140 or tricresyl phosphate with either mono- or diammonium-phosphate imparts llame retardance to melamine-urea-based intumescent coatings. Santolite Mill' is a useful plasticizer and flow aid. Synthetic Rubbers CHLORINATED RUBBER The performance of chlorinated rubber in coatings and in adhesives is usually enhanced by the presence of several Monsanto plasticizers, especially the Aroclor compounds. Chlorinated rubber-based coatings, because of their resistance to corrosive agents, moisture, fungus, mold, and other deteriorating environments, are widely used on masonry floors, walls, and swimming pools; on chemical plants; on railroad and marine equipment; and on highways, for traffic markings. The Aroclor plasticizers primarily increase resistance to acids, alkalies, salt water, and moisture; but they also impart adhesivity, improve cold-check resistance and weatherability, and make softer films. Other Monsanto plasticizers useful in chlorinated-rubber coatings include Santicizer B-16, triphenyl phosphate, tricresyl phosphate, and Santolite MHP. Aroclor plasticizers are used in chlorinated rubber-based heat-sealing adhesives that have chemical resistance and low moisture-vapor transmission. STYRENE-BUTADIENE COPOLYMERS Styrene-butadiene copolymers are widely used in enamels, maintenance finishes, exterior masonry paints, aluminum coatings, wall sealers, paper coatings, and printing inks. The Aroclor compounds are the most commonly used plasticizers for styrene-butadiene resins, but Santicizer B-16, Santicizer 160, dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate are also useful. NEOPRENE Aroclor plasticizers impart flame retardance to neoprene compositions. A small amount of Aroclor 1268 added to neoprene imparts excellent working qualities for injection moldings. Neoprene modified with Aroclor compounds is very useful as wire and cable coatings. Aroclor 5460 imparts plasticization and adhesivity to neoprene-based protective and decorative coatings that are commercially used on rubber products. 0212650 17 TOWOLDMONOQ25434 POLYBUTENE Mixtures of Aroclor plasticizers and polybutenes make permanently tacky coatings for fabric or paper. Such coatings are used for tape and sign backing, auto-body and windshield mastics, and foundrycore seals. NITRILE RUBBER Plasticizers are essential to modify many characteristics of nitrile rubbers. They improve processability, increase softness, reduce modulus of elongation, improve low-temperature properties, reduce volume change during immersion of vulcanizates, and lower the finishedproduct costs. Monomeric esters, such as Santicizer 160, dioctyl phthalate, and dioctyl adipate are good softeners, have pleasant odors, and impart improved low-temperature properties. Polyesters, such as Santicizer 409 and Santicizer 411, impart good physical properties, low volatility, and resistance to extraction by oils and solvents. Compatibilities of common plasticizers in nitrile rubbers are as follows: Compatibility Compatibility Plasticizer (.PHR) Plasticizer (PHR) Santicizer 160 100 Dioctyl adipate 20a Dioctyl phthalate 50 Diisodecyl adipate 33 Diisodecyl phthalate 33 Tricresyl phosphate 33 Santicizer 160 100 Santicizer 140 33 Santicizer 409 50 Santicizer 141 40 Santicizer 411 50 Santicizer B-16 50 HB-W 50 o) incompatible in higher-molecular-weight nitrile rubbers Performance of these plasticizers in nitrile rubber is compared in Table IV. Tensile strength, elongation, hardness, and modulus at 300- and at 500-per cent elongation are presented in Table V. Effects of aging (Table VI) and of solvent extraction (Tables VII and VIII) on these properties are also tabulated. The adipates are the most efficient plasticizers for nitrile rubbers (especially on low-temperature flexibility), followed closely by diiso decyl phthalate, dioctyl phthalate, and HB-ltO. Santicizer 140, Santi cizer B-16, tricresyl phosphate, Santicizer 160, and dibutyl phthalate is the least-efficient group of plasticizers. None of the plasticizers significantly affect either cure rate or tensile strength. The decrease in elongation is much less than the 50 per cent allowed by ASTM method 735-55T, and the hardriess increase for all plasticizers is less than the 15 points allowed. Stocks containing any of these plasticizers meet the B-suffix requirement under ASTM method D735-55T (35 per cent maximum). oz**b*' i i I ! 0I TOWOLDMONOQ25435 TABLE IV -- Performance of Plasticizers in Nitrile Rubber0 Properly Incorporation on Roll Mill (minutes) Mooney plasticity Large rotor, 212F Initial 1 minute 2 minutes 3 minutes 4 minutes 5 minutes Compatibility (surface description: hung in air 36 days) Low-temperature flexibility 5 hours, -40F 5 hours, -65F Compression set, % Cure, 45 min., 310F ASTM Method B, 70 hr., 212F Dibutyl Phthal- ate 18 Dioctyl Phthal- ate 19 Diisodecyl Phthalate 18 Santieizer 160 20 Dioctyl Adipate 20 Dii$0` decyl Adipate 19 Trlcresyt Phos phate 16 Santicizer 140 18 Santicizer 141 18 HB-40 19 89 90 86 100 83 83 94 98 98 86 70 68 65 77 63 63 72 80 71 67 63 60 59 67 57 55 65 75 62 60 60 55 56 62 53 52 61 67 58 58 58 53 53 58 50 50 59 62 56 56 58 53 52 57 50 50 58 59 54 55 Dry Dry Dry Dry Very Very Slight Very Dry Very slight slight tack slight slight tack tack tack tack Flexible Flexible Flexible Flexible Flexible Flexible Flexible Flexible Flexible Flexible Stiff Stiff Stiff Stiff Flexible Flexible Stiff Stiff Stiff Stiff 27.9 30.6 30.6 27.9 27.9 28.8 27.2 27,2 26.5 29,2 a) Formulation: Ingredients Ilycar* 1042 nitrile rubber Plasticizer FEF black Zinc oxide Stearic acid Tkiurad** activator Sul/asan** anti-aging compound cure: 20 min. at 810F Parts by Weight 100 15 50 5 1 0.8 0.8 Trtdtmirk of 6. f, Goodrich Co. Thlund md Sulttun n* tridomirki ol Montmlo Co., lotliUrtd In tho U. S. Pittnl Whe. QjlibS? 19 TOWOLDMONOQ25436 TABLE V -- Effect of Plasticizers on Physical Properties of Nitrile Rubber" Plasticizer (15PHR) Dibutyl Phthalate Dioctyl Phthalate Diisodecyl Phthalate Santicizer 160. Dioctyl Adipate Diisodecyl Adipate Tricresyl Phosphate Santicizer 140 Santicizer 141 Santicizer B-16 HB-40 Modulus at 300% Elongation (psl) 1100 1130 1170 1200 1030 970 1290 1240 1150 1260 1150 Modulus at 600% Elongation (psl) 2070 2100 2060 2265 2110 2070 2370 2280 2180 2280 2170 Ultimate Tensile Strength (psl) 2210 2220 2310 2400 2280 2280 2540 2420 2360 2400 2320 a) Formulation and curing: same as for Table IV (%) Elongation 570 560 590 565 565 595 600 560 575 575 575 Hardness (Shore "A") 52 54 54 55 52 52 57 57 56 56 ` 56 $ TABLE VI -- Effect of Plasticizers on Aging of Nitrile Rubber" (After aging for 70 hours at 212F) Plasticizer (15 PHR) Dibutyl Phthalate Modulus at 300% Elongation (psl) 2040 Ultimate Tensile Strength (psl) 2930 Dioctyl Phthalate 1850 2770 Diisodecyl Phthalate 1760 2700 Santicizer 160 Dioctyl Adipate 1870 1870 2830 2780 Diisodecyl Adipate Tricresyl Phosphate Santicizer 140 Santicizer 141 Santicizer B-16 HB-40 1770 1910 1920 1790 2030 2040 2675 2890 2710 2850 2700 2910 a) Formulation and curing: same as for Table IV Elongation (%> 435 450 450 450 445 455 460 415 455 450 420 Hardness (Shore "A") 67 61 60 63 60 59 62 64 62 63 68 TOWOLDMONOQ25437 TABLE VII -- Effect of Plasticizers on Oil Resistance of Nitrile Rubber0 (After immersion in #1 ASTM Oil for 70 hours at 212F) Plasticizer (15PHR) Dibutyl Phthalate Dioctyl Phthalate Diisodecyl Phthalate Santicizer 160 Dioctyl Adipate Diisodecyl Adipate Tricresyl Phosphate Santicizer 140 Santicizer 141 Santicizer B-16 HB-40 Modulus at 300% Elongation (psi) 1630 1540 1630 1730 1580 1520 1760 1725 1680 1720 1560 Modulus at 600% Elongation (psi) -- 2820 2750 2860 2725 2860 2860 2890 2740 2780 Ultimate Tensile Strength (psi) 2775 Elon gation (%) ' 495 2900 530 2750 500 2860 500 2725 480 2725 500 2860 500 2860 500 2950 515 2740 500 2780 500 a) Formulation and curing: same as for Table IV Hard ness (Shore "A") 55 55 55 55 58 58 58 55 56 58 59 Volume Change (%) - 7.0 -7.0 -6.9 -5.8 -7.3 -6.8 -4.6 -5.1 -5.8 ' -6.1 -7.4 TABLE VIII -- Effect of Plasticizers on Oil Resistance of Nitrile Rubber0 (After immersion in #3 ASTM oil for 70 hours at 212F) Plasticizer (16 PHR) Dibutyl Phthalate Modulus at 300% Elongation (psi) 1210 Modulus at 600% Elongation (psi) 2320 Ultimate Tensile Strength (psi) 2550 Dioctyl Phthalate Diisodecyl Phthalate Santicizer 160 Dioctyl Adipate Diisodecyl Adipate Tricresyl Phosphate Santicizer 140 Santicizer 141 Santicizer B-16 HB-40 1250 1230 1370 1200 1140 1420 1250 1320 1370 1220 2350 2490 2360 2430 2500 2500 2370 2460 2370 2510 2620 2700 2530 2640 2480 2530 2520 2570 2360 2520 a) Formulation and curing: same as for Table IV Elon gation (%> 555 535 520 500 515 535 510 540 510 515 535 Hard ness (Shore "A") 46 46 46 46 46 46 49 46 46 48 48 Volume Change (%) 4 7.5 +6.5 4 7.2 + 8.3 4 7.2 4-7.0 ^ 9.0 4 8.7 4 8.5 4 7.5 4 7.4 21 TOWOLDMONOQ25438 POLYSULFIDE RUBBERS Thiokol* polysulfide liquid polymers are easily converted "in place" to rubbery materials. Cured polysulfide rubbers are noted for outstanding oil and solvent resistance, excellent weatherability (oxygen, ozone, and light), good electrical insulation properties, resilience, and broad service-temperature range. They are used in sealants, casting and potting compounds, adhesives, and coatings--often in combinations with epoxy or phenolic resins. Several Monsanto plasticizers and modifiers enable the formulator to obtain the benefits of these useful materials at economical costs. Joint-Sealant Compounds Polysulfide-based adhesives are increasingly used as joint sealants in curtain-wall construction and in airport runways. They are also widely used in jet fuel-resistant coatings and in skid-resistant surfaces on bridges and highways. Liquid Aroclor compounds, such as Aroclor 1232, are excellent viscosity- and cost-reducing modifiers, at concentra tions of about 15 PHR, for sealant compounds. Casting Compounds Since they do not swell when in contact with solvents, polysulfide-based casting compounds are well suited for printing-press rolls, solventresistant gaskets, and similar cast products. Either Santicizer 160 or an Aroclor plasticizer may be used at a concentration of about 40 PHR to modify polysulfide casting compounds. Liquid Aroclor com pounds lower casting viscosity and raise filler tolerance, whereas the solid Aroclor compounds are used where the lowest volatility is required. Polysulfide-Epoxy Combinations Mod-Epox is used to reduce the viscosity of uncured polysulfide-epoxy resin mixtures for easier handling. It also increases the bond strength, reduces the curing-agent requirements, and lowers the overall costs, without adversely affecting other properties of the compound. Aroclor plasticizers, HB-bO, and Santicizer 8 are also used in polysulfide-and-epoxy-based concrete-patching formulations and adhesives to reduce viscosity and lower cost. SILICONE RUBBER Aroclor compounds are very effective flame retardants for silicone rubbers. *Tnd*mtrk of Thiokol Chooileol Co. I t TOWOLDMONOQ25439 Polyvinylidene Chloride Vinylidene chloride homopolymers and copolymers have excellent chemical resistance and low moisture-vapor- and gas-transmission rates. In some applications no plasticizer is needed, but in textile and paper coatings a plasticizer is required to impart the desired flexibility. Since any plasticizer reduces chemical and moisture-vapor resistance, the selected plasticizer must be efficient. The phthalyl glycolates (Santicizer B-16, Santicizer E-15, and Santicizer M-17) are very efficient. So are Santicizer 141, Santicizer 160, dioctyl phthalate, and diethyl phthalate. Performance of several plasticizers in Saran resin (vinylidene chloride-vinyl chloride copolymers) are shown in the following table. TABLE IX -- Evaluation of Plasticizers in Saran0 Relative Compatlbillty'' Vola tillty (87C 2 hr.) Plasticizer lost (%) Solvency Santicizer B-16 6% Plasticizer 0 10% Plasticizer 0 B% Plasticizer 6.1 Dioctyl Phthalate 0 3 7.8 Santicizer 160 1 2 5.7 Santicizer E-15 3 0 10.1 Santicizer 213 4 4 5.3 Aroclor 5460 5 0 4.6 Santicizer 141 8 7 7.1 10% Plasticizer 13.8 7.8 12.4 18.0 11.8 0.7 10.7 Precipitation Rating Temp. (C) Hot Solvent 130 Hot ` 96 Solvent Hot Solvent 92 Non Solvent -- -- -- -- -- Hot Solvent 69 a) Saran resin B-118, Dow Chemical Co. b) On a relative scale from 0 no exudation to 10 incompatible Completely nontoxic Santicizer E-15 and Santicizer B-16 are excellent plasticizers for Saran. In hot-melt, extruded-paper coatings, they aid in heat sealing and impart improved low-temperature flexibility. In solvent-cast Saran-resin solutions, plasticizers impart improved flex ibility and aid in solvent release. Generally, only small percentages of the plasticizer are required to produce a high degree of softness and elongation. For example, films containing 25-per cent Santicizer B-16 with Saran F-120 resin have greater than 300-per cent elongation. Vinylidene chloride latexes, such as Dow latex 744-B are used in paper coatings. Plasticizers are essential to laydown of continuous, pinholefree films. Plasticizers that accelerate fusion of latex particles aid in giving a pinhole-free coating. Strongly solvating plasticizers aid in heat sealing. Santicizer 141 is excellent in these respects and is superior to 02126*6 23 TOWOLDMONOQ25440 both dioctyl phthalate and tridresyl phosphate. Plasticizers generally impart to vinylidene chloride latexes the same properties they impart to polyvinyl chloride resins. Efficient Monsanto plasticizers aid in heat sealing and impart flexibility, softness, and elongation to potyvinylidene chloride barrier coatings on packaging films. A starting point for a clear coating for paperboard containers is as follows: CLEAR COATING FOR PAPERBOARD CARTONS Ingredients % Solids )ow Latex 744-B 50 Santicizer 141 emulsion" 50 Methocel* (15 cp.) methyl cellulose 5 Dry Wet (parts by weight) 100 200 18 36 0.6 1.2 a) Phase A Santicizer 141 Oleic acid Parts by Weight 50 3 Phase B 28% Aqueous ammonia Water 1 46 Phase B is added slowly to phase A during high-shear agitation. A water-in-oil emulsion forms first, and addition of more water phase inverts it into the desired oil-in-water emulsion. TikStmttV, Cow Ctitmtul Co. ' ' 0212 6^7 24 TOWOLDMONOQ25441 A clear wallpaper coating can be produced with Santicizer 141 added without emulsification. A starting formulation is: CLEAR, WASHABLE WALLPAPER COATING Ingredients Dow Latex 744 B Phos-Chek* P/30 Sylon* 200 colloidol silica Parts by Weight (dry) 100 25 19 Scrub-resistant intumescentcoatings for low-density fiber wallboard and acoustical tile are based on vinylidene chloride-vinyl chloride copolymer latexes. Santicizer 141 and dioctyl phthalate are the recom mended plasticizers for such coatings. A suggested starting formula is as follows: INTUMESCENT COATING Grind in Pebble Mill: lbs. gals. Water Potassium Tripolyphosphate Surfactant on Wetting Agent Phos-Chek* P/30 Melamine Dipentaerythritol Phenyl Mercuric Acetate Anti-foaming Agent Titanium Dioxide Chlorinated Paraffin (70% Concentration) 290.0 3.0 4.0 260.0 80.0 75.0 0.5 3.0 60.0 40.0 34.8 0.3 0.4 17.3 6.8 6.4 .-- 0.3 1.8 2.9 Then Add Slowly with Agitation: Methocel** (50 cp) (5% solids) Dow Latex 744-B (50% solids) Anti-foaming Agent Santicizer 141 45.0 220.0 1.0 3.4 5.2 24.2 0.1 -- The solvating, plasticizing, or swelling action of liquid plasticizers on the polymer at room temperature seriously reduces the mechanical stability of the latex. Solid plasticizers, such as diphenyl phthalate, triphenyl phosphate, and Santicizer 9, however, can be added to part I before milling, since they do not exert any solvating effect until the temperature exceeds their melting point (U. S. Patent No. 2,917,476). The amount of solid plasticizer recommended is from 5- to 25-per cent of the polymer solids. The resulting coating has the abrasion resistance, scrub resistance, and fire-retardancy desired. Polyvinylpyrrolidone Polyvinylpyrrolidone is a water-soluble, film-forming resin that when unmodified dries to form hard, clear, transparent, glossy films. Com patible plasticizers may be added to alter hardness, to control tack or brittleness, and to decrease hygroscopicity. Trdmrk l Monunte Cwnpiny Tuttomirk ef Dow Chomktl CornMny 25 TOWOLDMONOQ25442 Compatibility limits of several plasticizers in polyvinylpyrrolidone are as follows: Compatibility Plasticizer (PHR) Dimethyl Phthalate 100 Santicizer E-15 100 Santicizer 141 33 Santolite MHP 11 Essentially tack-free films at any relative humidity are obtained by the addition of 10-per cent Santolite MHP. Dimethyl phthalate functions at a relative humidity of as high as 70 per cent, whereas Santicizer E-15 is an effective plasticizer at relative humidities lower than 50 per cent. A more important use for plasticizers is in vinylpyrrolidone-vinyl acetate copolymers. Some of the end uses are in pressure-sensitive adhesives, rewettable adhesives, hair-grooming agents, white shoe polishes, and antitarnish coatings. Monsanto plasticizers compatible with vinylpyrrolidone-vinyl acetate copolymers include: dimethyl phthalate dibutyl phthalate Santicizer B-16 * Santicizer E-15 Santicizer 141 Santicizer 213 Santolite MHP Generally 1:1 ratios of copolymer and compatible plasticizers yield adhesive, tacky, pressure-sensitive films. Such compositions adhere to polyester film, cellophane, cellulose acetate, kraft paper, urethane sponge, aluminum foil, glassine,and Saran. Excellent adhesive coatings with good adhesion to glass, aluminum, and nylon are the following suggested formulations: FORMULATIONS FOR PRESSURE-SENSITIVE-ADHESIVE COATINGS Ingredients Vinylpyrrolidone-vinyl acetate copolymer" Opalon* 440 PVC resin Vinylite** VYHH PVC resin Dioctyl phthalate Methyl ethyl ketone Toluene Plastisol Organosol (parts by weight) 100 100 300 -- -- 100 200 15 -- 200 -- 200 a) 1-535, General Aniline & Film Corp. To improve flexibility and reduce hygroscopicity, dimethyl phthalate may be added to hair grooming formulations (10- to 25-per cent based Option It t Monttnlo Compiny litdomtrk, railittrod In the U. S. Pltont 0!ft Tftitmtik ot Union Ctrbldt Corp. $I I 0212659 I ! 26 TOWOLDMONOQ25443 on resin solids). The following formulations are typical: SUGGESTED HAIRGROOMING FORMULATIONS Women's Men's Hair Wave Set Hair Spray Dressing Ingredients (parts by weight) Vinylpyrrolidone-vinyl acetate copolymer0 Dimethyl phthalate Santicizer E-15 Lanolin derivative Silicone fluid Isopropyl myristate 100 -- 5-12.5 2- 5 -- -- 100 2.5 -- 12.5* 6.25 -- 100 2.! -- 25* -- 500 Perfume Ethanol (absolute) Ethanol (95%) Propellant (difluorodichloromethane) 95 -- 900 -- 6.25 372 -- 2000 25 1845 -- 10,000 ) E-735, General Aniline & Film Corp. ) Lanogel 41, Robinson-Wagner Co. Protein Resins Protein materials such as casein, zein, allyl starch, and soya protein require special plasticizers. The following Monsanto products are plasticizers for these materials: Primary Santicizer 3 Santicizer 8 Santicizer 9 Santolite MHP Santolite MS-80% Secondary Triphenyl Phosphate Tricresyl Phosphate Dibutyl Phthalate Santicizer 160 Aroclor Compounds Santicizer B-16 CASEIN Casein is a conjugated phosphoprotein obtained from milk. Its use in surface coatings has been fairly well established, mainly as a protective colloid, binder, and stabilizer for emulsion paints. In some applications unmodified casein is used. In others, the casein is modified and dissolved in water; formaldehyde is added to form a film that, when dry, is fairly water resistant. Unmodified casein can be dissolved in water in the presence of a suitable alkaline medium such as ammonia, morpholine, or 2-amino-2-methyl-l-propanol. The use of these volatile alkaline agents to dissolve casein results in improved washability of the film when completely dry. In addition, dissolving the casein in ammonia improves the shelf life of casein solutions. Santicizer 9, very compatible in casein coatings and adhesives, permits greater tolerance of formaldehyde without causing reversable gels. It 0212660 27 TOWOLDMONOQ25444 I also imparts some flexibility to the coatings. With Santicizer 9, casein coatings and adhesives are less viscous than those dissolved in ammonia alone. In addition, Santicizer 9 improves the smoothness of pigmented material. Molding powders containing casein (67 to 68 per cent), Santicizer 9 (20 per cent), formaldehyde (2 to 3 per cent), and water (10 per cent) are compression molded into buttons. Santicizer 8 in casein improves flexibility, water resistance, gloss, and adhesion and is compatible in molding compositions to at least 50 PHR. Santicizer 8 (at a concentration of 67 PHR in an aqueous-ammonia solution of casein) provides excellent flexibility and scuff and grease resistance in grease-proof-paper coatings. Santicizer B-16 and Santolite MS-80% make satisfactory emulsions with casein. ZEIN Zein, an aqueous-alcohol-soluble corn protein, is a high-molecularweight polymer composed of amino-acid groups united by peptide linkages. Solutions of zein in organic solvents or aqueous systems are adaptable to a wide range of coatings, film, fiber, and ink applications. The high proportion of amide and non-polar side chains accounts for its solubility in many organic solvents. The only industrially available protein soluble in organic solvents, it is soluble in the lower aqueous alcohols, glycols, and glycol ethers. Solvents for zein generally contain at least one functional group (hydroxyl, carbonyl, amide, or amine). Secondary solvents (which do not dissolve zein but which enhance its solubility in a primary solvent) include lower ketones, aliphatic esters, chlorinated hydrocarbons, and the higher glycol ethers. They permit modification of such properties of zein solutions as evaporation rate and viscosity. They also promote compatibility with various plasticizers and resins. Zein is insoluble in water but readily soluble in dilute aqueous solutions of strong alkalies (pH 9.5). Useful aqueous systems of zein are prepared with ammonium or sodium resinates and various synthetic detergents such as alkyl aryl sulfonates. Unlike other proteins zein is resistant to microbial attack. Films and coatings are tough, glossy, scufTproof, and grease resistant. Fibers have wool-like properties, high tensile strength, and notable resistance to acids, alkalies, and organic solvents. Although zein is compatible with a number of resins and plasticizers, Monsanto's highly-polar sulfonamide plasticizers- Santicizer 3, Santi cizer 8, Santicizer 9 -and sulfonamide-formaldehyde resins--- Santolite MHP and Santolite MS-80%--are considered the best available modifiers for zein. Blends of zein with plasticizers and natural or synthetic resins yield fusible compositions. Alcohol solutions of plasticized zein and a compatible resin are partic ularly adaptable to use as label and overprint varnishes that are tough, glossy, and scuff resistant. Santicizer 3 is perhaps the best plasticizer i 0212661 28 TOWOLDMONOQ25445 available for zein, in which it is highly compatible. Formulations plas ticized with Santicizer 3, sometimes in combination with Santolite MHP or rosin derivatives, are useful as decorative lacquers, release coatings for pressure-sensitive tapes, and hot-metal adhesives. Santicizer 8 improves flexibility, water resistance, gloss, and adhesion and is compatible to at least 50 PHli. In label varnishes it prevents curling of the label. Santolite MHP is compatible with zein and improves brilliance, adhe sion, and moisture resistance of zein compositions. The incorporation of Santolite MHP in protein compositions makes possible the use of plasticizers that are otherwise incompatible. Thus, fairly flexible compositions can be formed by the use of Santolite MHP, plus Santicizer B-16 equal to about half the weight of Santolite MHP. Santolite MHP markedly reduces viscosity and gelling of solutions of zein in 80-per cent isopropanol--20-per cent toluene. It also improves water resistance of cast zein films. Highly grease-resistant and grease-proof zein-based coatings can be applied to paper and paper board. Zein or zein-resin mixtures dissolved in alcohol or glycol are excellent vehicles for flexographic, moisture-resistant, or heat-set inks to which zein imparts rapid solvent release, hot or cold scuff resistance, hard ness, and excellent pigment binding. The stability of alcohol-based flexographic inks is greatly improved by addition of wetting agents to the zein vehicles before pigment milling. These inks strongly resist precipitation on absorption of atmospheric moisture. Deaminated zein dispersed in aqueous ammonia and plasticized with either Santicizer 8 or Santicizer 9 is gaining acceptance as a vehicle for water-based inks. Fusible resins, made by blending zein with other resins and Santicizer 8, may be either pelletized or powdered and mixed with fillers to form molding powders, or they may be dissolved in solvents to give coating solutions. Various zein coatings are grease proof, water resistant, and glossy; and they are applied to paper, glassine, cellophane, foils, and textiles (as sizing). ALLYL STARCH Substitution of the hydroxy-hydrogen atoms of the starch molecule by ally! groups produces allyl starch, which forms stable, cross-linked polymers. At least 20-per cent plasticizer is required to make the film flexible. Santicizer 8 is compatible in proportions greater than 20 parts per 100 parts of resin and is used with allyl starch in furniture finishes and grease-proof paper. The Aroclor compounds are highly compatible and very efficient plasticizers for allyl starch. Aroclor 1242 is mentioned in U. S. Patent No. 2,740,724 (assigned to the U. S. Dept, of Agriculture) as a suitable plasticizer for an allyl starch emulsion in a preferred pH range of 8 to 11. 0212662 29 TOWOLDMONOQ25446 A typical emulsion formulation is as follows: Ingredients Allyl Starch Aroclor 1242 Triton* X-100 Ammonium Hydroxide (cone.) Water Parts by Weight 100 25 6.25 4 210 The emulsion is stabilized by addition of sodium tetrahydronaphthalene sulfonate (Alkanol** S). Asphalt and Shellac ASPHALT The major benefits of Monsanto plasticizers in asphalt are to provide adhesion, tack, and flame retardancy. Aroclor 5460, at a concentration of 30 per cent, makes asphalt caulking, roof-coating, and sound-deadening-coating compositions self-extinguish ing. It also imparts adhesion and quick tack. Aroclor 5460 and HB-JfO are used together with asphalt to make sealers for asphalt roads. Montar*** compounds are also used to provide flame retardance. The Montar products are compatible with asphalt at ratios up to two parts for each part of asphalt. Both softening point and brittleness of the asphalt blend are increased as the concentration of Montar compound is increased. Blending is accomplished by thorough mixing, with heat if necessary. Montar 1 or 5 contributes flame retardance at concentrations as low as 10 per cent with instantaneous flame-out above 30 per cent. Flames are "snuffed" by an intumescent layer that forms on the surface of the mixture. Solutions of Montar 1 or 5 in molten asphalt were heated in a crucible until flames occurred (about 200 C). The times required for the flames to go out after removal of the burner are shown in Table X for various concentrations of Montar 1 or 5: TABLE X -- Effect of Montar 1 or 5 on Asphalt Flammability Concentration of Montar 1 or 6 (%) 0 10 20 30 50 67 Flame-Out Time (seconds) 210 90 10-20 Instantaneous Instantaneous Instantaneous SHELLAC Santicizer 8 increases the flexibility and definitely softens shellac with out impairing the adhesion of the resin. Santicizer 9 and Santicizer B-16 are also useful, although less effective than Santicizer 8. Tiadamark of Rohm t Hut Co. Tradamark of Ih* Du Pont Co. Tiadamark of Monunlo Company o2V,6b3 <1 | TOWOLDMONOQ25447 Plasticizer Council Perhaps your toughest, most urgent problem is not mentioned in this bulletin. Or maybe the suggested solutions do not completely meet your specific requirements. It may prove worth your while to present your problem and require ments to Monsanto's Plasticizer Council. With no obligation, you will obtain prompt attention; concentrated, experienced thought; skilled laboratory experimentation; thorough evaluation; and an unprejudiced recommendation. There are many sound reasons why it will pay you to consider Monsanto's Plasticizer Council as an extension of your own technical facilities- as many major plastics processors regularly do. As the pioneer in the art, technology, and science of plasticizing, Monsanto is uniquely organized to develop and capitalize on a team of research experts in all aspects and phases of plasticizer performance. Since Monsanto produces more different plasticizers and more different classes of plasticizers than any other company anywhere, the Plasticizer Council can (and always does) suggest the one best plasticizer system to meet your performance and cost requirements. You never need to worry about Monsanto promoting a particular plasticizer just because it happens to be a Monsanto specialty. Your best interests always govern our proposals. As you well know, new resins are being developed at an astoundingly rapid rate. Plastics are being tailored for more and more applications, and their performance requirements are becoming tougher. Just as you keep ahead in your major areas of technical competence, so Monsanto stays out in front in plasticizers. When new and better plasticizers are developed, Monsanto is most likely to be first with the best. The Monsanto system of assigning a team of researchers to all aspects of research on plasticizers, including new products, product and process improvement, and customer service, works to your definite advantage. Chemists working on your problem can bring to bear the latest research results and thinking, as necessary, as well as drawing on more than 30-years' accumulated experience and data. And their new-product and product improvement investigations are conducted in an environ ment of keen awareness of and appreciation for practical industrial needs. Whenever a new or better plasticizer system appears to be the key to the development of your new product, the improvement of your present product, or the solution to your processing problem, the experienced creativity of Monsanto's Plasticizer Council is at your service. For consideration of your problem, you may either contact the Monsanto sales representative who calls on you or write: Monsanto Company Plasticizer Council, Dept. PL-804 Organic Chemicals Division 800 North Lindbergh Boulevard St. Louis, Missouri 63166 021266* TOWOLDMONOQ25448 Technical Bulletins on Monsanto Plasticizers Detailed technical information about the properties and applications of the Monsanto plasticizers mentioned in this bulletin is included in the following Monsanto technical bulletins. We revise these bulletins as often as necessary to include the most up-to-date and reliable information possible. We will promptly send you any bulletins you request. Technical Bulletin No. Sulfonamides 0/PL-1H PL-3 O/PL-339 O/PL-9 O/PL-820 Phihalyl Glycolatc Esters PL-15 PL-16 PL-17 Phosphate Esters O/PL-805 PL-301 O/PL-140 0/PL-141 Phthalate Esters PL-302 PL-312 PL-303 PL-300 O/PL-342 PL-819 O/PL-347 O/PL-213 Adipate Ester PL-304 Other Plasticizers PL-409 PL-411 O/PL-313 PL-317 O/PL-828 O/PL-806 O/PL-311 General PL-807 PL-827 PL-331 O/PL-22 Title Santicizer 1-H Santicizer 3 Santicizer 8 Santicizer 9 Santolite MHP and Santolite MS-80 % Santicizer E-15 Santicizer B-16 Santicizer M-17 * Tricresyl Phosphate Triphenyl Phosphate Santicizer 140 Santicizer 141 Dibutyl Phthalate Dicyclohexyl Phthalate Diethyl Phthalate and Dimethyl Phthalate Diisodecyl Phthalate Dioctyl Phthalate Diphenyl Phthalate Santicizer 160 Santicizer 218 & 214 Dioctyl Adipate Santicizer 409 Santicizer 411 Mod-Epox Triphenyl Phosphite Montar Compounds Aroclor Plasticizers Aroclor resins and plasticizers for chlorinated rubber Monsanto Plasticizers in Synthetic-Resin Adhesives Monsanto Plasticizers in Protective Coatings Monsanto Modifiers for Thiokol Polysulfide Liquid Polymers Phosgard C-22-R 021 ?t65 m 0 Z bl 1 z o o Of D O > Of o It. ^Ul Of < (A o 0! < o > -I Q. Ill Of U (A Ul X h- Gentlemen: (dtte) Please send me a copy of each indicated technical bulletin containing additional detailed information about Monsanto plasticizers for hard-to-plasticize PO PL-_ < PL-. 2 Comments- x o Name_ Title- < Company. o Address__ 5 City_____ X State- o Ul PL-. PL-_ PL-_ PL-_ _Zone_ Gentlemen: (date) Please send me a copy of each indicated technical bulletin containing additional detailed information about Monsanto plasticizers for hard-to-plasticize resins: PL-PL-_ PL-_ PL-- PL-_ PL-_ Comments- NameTitle-- CompanyAddress__ City_____ State- -Zone- <zo p 5 Gentlemen: (date) Gentlemen: (date) a Please send me a copy of each indicated technical Please send me a copy of each indicated technical < bulletin containing additional detailed information bulletin containing additional detailed information about Monsanto plasticizers for hard-to-plasticize about Monsanto plasticizers for hard-to-plasticize a resins: PL-........ .... < PL-______ h Comments.. 00 o Name_ TitleCompanyAddress__ City_____ State PL-. PL-. PL-PL-. -Zone- PL-_ PL-Comments- PL-_ PL-. PL-_ Pl^_ NameTitle. CompanyAddress__ CityState- _Zone_ 0212666 O/Pl 332A. TOWOLDMONOQ25450 BUSINESS REPLY MAIL MONSANTO COMPANY PLASTICIZER COUNCIL, DEPT. 804 Organic Chemicals Division 800 North Lindbergh Boulevard St. Louis, Missouri 63166 FIRST CLASS Pormff No. 3016 ST. LOUIS. MO. BUSINESS REPLY MAIL MONSANTO COMPANY PLASTICIZER COUNCIL, DEPT. 804 Organic Chemicals Division 800 North Lindbergh Boulevard St. Louis, Missouri 63166 FIRST CLASS Pormtf No. 3016 ST. LOUIS. MO. mm BUSINESS REPLY MAIL MONSANTO COMPANY PLASTICIZER COUNCIL, DEPT. 804 Organic Chemicals Division 800 North Lindbergh Boulevard St. Louis, Missouri 63166 FIRST CLASS Pormlt No. 3016 -- -- " : ' BUSINESS REPLY MAIL MONSANTO COMPANY PLASTICIZER COUNCIL, DEPT. 804 Organic Chemicals Division 800 North Lindbergh Boulevard St. Louis, Missouri 63166 FUST Cl> Pormrt No. ST. LOUIS. 0212667 PLEASE REQUEST SAMPLES ON YOUR COMPANY LETTERHEAD *4 TOWOLDMONOQ25451 0212t><>8 Monsanto too N. LINDBERGH BLVD., ST. LOUIS. MISSOURI 03116 TOWOLDMONOQ25452