Document 9L97VQEeKOXXr0deLOdX4N8DR

K' Monsanto! kA i $MM&; '?( ff{i$ WS^l jVv ... ,K,s - M it ffc 1 |; V l: /* ,- ]{.*'. ;^V: t?y 0508574 TOWOLDMONOQ34137 CONTENTS INTRODUCTION ........................................... ....................................... GUIDE TO MONSANTO PLASTICIZERS EOR HARD-TO-PLASTICIZE RESINS .................................. ACRYLIC RESINS ............................................................................... EPOXY RESINS ..................................................................................... POLYESTER RESINS ...!...................................................................... POLYAMIDE RESINS ..................... ................................................... PHENOLIC RESINS ........................................................................ ..... MELAMINE RESINS ........................................................................... SYNTHETIC RURBERS !................................................................... POLYVINYLIDENE CHLORIDE ................... 1................................. POLYVINYLPYRROLIDONE ............................................................ PROTEIN RESINS ............................................................................... ASPHALT AND SHELLAC ................................................................ PLASTICIZER COUNCIL..................................................................... TECHNICAL BULLETINS ON MONSANTO PLASTICIZERS 1 2 4 6 9 11 13 15 22 25 27 30 31 32 The information contained in this bulletin is. to our be:t knowledge, true and accurate, but all re commendations or suggestions aro mado without guarantee, since the conditions of use are beyond our control. The Monsanto Chemical Company disclaims any liability incurred in connection with the use of these data or suggestions. Furthermore, nothing contained herein shali be construed as a recommendation to use any product in conflict with existing patents covering any material or its uso. 0508575 TOWOLDMONOQ34138 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 plasticiz ers for many other resins, especially some of the thermosetting resins, that are more difficult to plasticize satisfactorily. Many formulalors require just the right plasticizer to improve the per formance of a particular resin in an existing application, to make it suitable for a new applica tion, 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-cighty plasticizers. Monsanto's Plasticizer Council, with its years of cumulative experience with virtually every kind of commercial resin, offers unmatched com petence and know-how with which to seek and find answers to the toughest plasticizing re quirements. This bulletin has been prepared to give you some idea of the breadth and versatility of Mon santo'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 belter plasticizer. For more detailed information, we will gladly send you Monsanto technical bulletins on indi cated plasticizers or on the general application area. Of course your specific inquiry to the Plasticizer Council, directed either to the nearest Monsanto District Sales Office or to the Plasticizer Sales Department in St. Louis, will receive prompt, expert attention. \ I Gi>06b76 TOWOLDMONOQ34139 GUIDE TO MONSANTO PLASTICIZERS ; FOR HARD-TO-PLASTICIZE RESINS O' PJaiflcirer Acrylic Epoxy Polyester Poly mlde dimer acid' nylon based Phenolic Melamine Chlormated rubber StyreneButadiene Neoprene Phthalates dibutyl dicyclohcxyl diethyl diisodccy) dimethyl dioctyl diphenyl Santicizer* 160 Santicizer 165 Santicizer 215 XX X X X X X X X X X X X XX X XX Adipates diisodccy] dioctyl Phosphates Tricresyl Triphcnyl Santicizer HO Santicizer HI Glycolete* Santicizer E15 Santicizer B'16 Santicizer M*17 XX XX XX X XX X X XXXX X X i XX Sulfonamides Santicizer i*H Santicizer Santicizer 8 Santicizer 9 Santolite* MHP Santolite MS'80% XX XX X XX X X XX X X XX XX XX Other HB-40* X MoD'Eeox* X Triphcnyl Phosphite X Montar* Aroclor* Santicizer 409 1721 1254 1246 12(0 (4(0 12(2 X 12(0 44(5 54(0 X 12(0 54(0 25(5 12(7 X X 12(1 54(0 Santicizer 411 Santicizer, Santoi.jte, HB-40, Mod-Epox, Montar, and Aroclor arc Monsanto Chemical Company trademarks, registered in the U. S. Patent Office. 05085/7 TOWOLDMONOQ34140 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 con stantly 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 Nitillo butene rubber Poly sulfide PolyvinylSilicone Crepe idene rubber rubber chloride Vinylpyrrolidone Vinyl Homo Acetate polymer Copolymer Casein Zein * Soye Ally! starch Shellac Asphalt X^ X X X XXXX X X XX XX X X X XXXX X X X X X X x XX XXX X XXXX X XX X X X X XXXXX X X X -X X X X X X X 1222 X 12*2 M*0 XX XX X XX XX .X X X XXXX 4 M&O i>08578 3 TOWOLDMONOQ34141 ACHYLIC RESINS Polymers of acrylic and mcthacrylic acids and esters are noted for their clarity and outstanding light and weather resistance. They are widely used in extrusions, sheet, injection moldings, east ings, fibers, and adhesives. A major expanding use of acrylic resins is in solution coalings, where they impart exceptional durability, light-fastness, hardness, and high gloss upon polishing. Since acrylic and acrylicmodified 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, furni ture, 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 sensivity to moisture and high humidity; improve economics by extending the more costly resin; and have the least effect on the desir able 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 characteris tics. Acrylic coatings plasticized with Santicizkr 160 offer excellent adhesion, gloss, humidity compatibility, levelling, flexibility, light stability, and cold-check resistance. Dicyclohexyl phthalatc is sometimes used with Santicizer 160 to achieve harder lacquers and (o 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 volatiliza tion. In Monsanto's continuing research and development programs to produce evcr-bellcr plasticiz ers, 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 1. (Plus signs indicate that the plastizer performs better than Santicizer 160 in the indicated property; minus signs denote poorer per formance.) 0 0?' A 0808879 TOWOLDMONOQ34142 TABLE I--PLASTICIZER PERFORMANCE IN ACRYLIC RESIN Plasticizer NONE Santicizer 160 Dimthyl Phthalate Diethyl Phthalate Di'outyl Phthalate Dioctyl Phthalate Diisodccyl Phthalate Santicizer 165 Santic'ZER B'16 Dicyclohexyl Phthalate DCHP/Santicizer 160 (2/1) DCHP/Santicizer 160 (1/2) Tricresv! Phosphate Santicizer 140 Santicizer 141 Santicizer 409/Santicizer 160 (2/1) Santicizer 409/Santicizer. 160 (1/1) Santicizer 409/Santicizer 160(1/2) Solvency4 Standard 4- 4- 4equivalent -- -- equivalent -- -- -- -- equivalent -- -- Volatility^ (I00"C. 23 hr.) Plast. Lost (%i 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 . 27.5 Repairafeillty4 (Solvent Craze) .---------Standard + -- -- equivalent 4-4- slight neg. 36.3 slight neg. Humidity^ Stability equivalent Standard -- -- -- -- -- -- -- equivalent equivalent Light* Stability (gloss) 84 78 (Std) 67 80 80 67 75 71 a) Solvency compared to that of Santicizer 160 in one or more of three wavs: film solvation, gel temperature of plastici2er*resin mixture or of plasticized'lacquer system, and viscosity of plasticized lacquers. b) Values for volatility may also include solvent loss because of poor solvent release. c) Comparison of observed checking after either 3'minute immersion of ' pjasticized'lacqucr 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 40*C for 100 hours, then panels rated according to ASTM test D'714. e) Flasticizeddacbuer films on glass panels exposed in V/eather'Omcter* for 125 hours, then gloss measured (highest values are best). Trademark of Atlas Electric Devices Co. 0 8 S 9 0 < iO TOWOLDMONOQ34143 3 /jj fEPOXY RESINS Epoxy resins generally are chemically resistant, flexible, tough, and adhesive. Available as solids, liquids, or solutions, they arc useful in surface coatings, including chemical-resistant coatings, maintenance coatings, baking finishes, and laminates; in adhesives; and in encapsulation, potling, lamination, and casting compounds. Plasticizers are not ordinarily used in epoxy resins when maximum performance is desired. Pccause 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 (hem easier to handle. Performance evaluations of several Monsanto plasticizers and reactive diluents for epoxy resins are tabulated in Table II. APPLICATIONS Surface Coalings In surface coatings, the use of Aroclor 1254, Aroclor 1260, or Arocj.or 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 plasti cizers 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 prop erties, Mod-Epox and Santicizer 8 are suggested for use in epoxy encapsulating, potiing, lami nating, and casting compounds. 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, Santjcizer Ii-16, Aroclor 1221, Santicizer E-15, dibutyl phlhalate, tricresyl phosphate, Santici/i:r 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 adhcsivily. 4 OSOBiBi TOWOLDMONOQ34144 TABLE !!--PERFORMANCE OF MONSANTO PLASTICIZERS AND REACTIVE DILUENTS IN EPOXY RESINS Viscosity* None (control) Dibutyl Phthalatc SANTtCIZER E-15 Savticizer M'17 Santicizer B-16 Tricrcsyl phosphate Santictzer MO Santjcizer Ml Aroclor 1248 Aroclor 1221 Mod-Epox Santictzer 8 Before Adding Curing Agent (cp) 12,800<* 1550 3050 3150 2300 3750 2850 . 1500 7700 1650 1650 7600 After Adding Curing Agent Wp) 7900 1300 2100 2450 2000 3000 2200 MOO 4300 1200 . 1250 3100 a) Formulation Ingredients Epoxy Resin Plasticiser Tetracthylenepentamine Parts 100 25 8 Physical Properties Physical Properties After Cure (0.5 hr @ 100*C) APer Heat Aging (24 hours <) 87*C in activated carbon) tiod Impact Resistance Clarity; light Hardnoss, - reflected Shore "0" (%) . . (10 sec) Hardness Shore "D" (10 see) Weight Change (%) 0.2 -- -- -- -- -- -- -- 0.6 .-- 0.8 0.9 0.2 3.0 3.5 2.5 3.0 4.5 3.5 3.5 4.0 3.0 3.0 4.0 3.0 78 86 --0.012 10 78 --0.734 10 80 0.119 6 85 --0.131 7 85 --0.013 15 86 -- 0.222 22 79 --0.284 5 82 ---0.425 40 88 --0.682 8 81 --2.118 84 88 0.134 84 ' 88 , --0.007 O oo b) All are compatible in the liquid resin and in the cured resin; both at room temperature and after 0.5 hour c) Brookfield LVF #4 spindle: 60 rpm unless otherwise specified d) 30 rpm * O hr TOWOLDMONOQ34145 Flammability and cost- two major limitations of epoxy resins--arc diminished through the use of Akoclor compounds: nonburning compositions are made by the use of an Akoclor compound (15 PUR) ami antimony oxide (5 P11R). About one-fourth the cost of epoxy resins, Akoclor plasticizers permit significant cost reduction. The use of the liquid Akoclor plasticizers (1221 and 1248) in aliphatic amine-cured epoxies also improves flexural strength and compressive-yield strength, has little effect on tensile strength, and only slightly lowers heat-distortion temperature and ultimate compressive strength. They arc commonly used in solvenllcss coatings. ' Solid Akoclor compounds (1262 and 5460) greatly improve compressive strength, compressiveyield strength, flexural strength, and tensile strength; although they slightly lower the heat dis tortion temperature. They are used, sometimes in combination with liquid Akoclor plasticizers, in solvent-containing coatings. Extension of epoxy-resin adhesives with Akoclor compounds greatly reduces the formulation cost and has minimum effect on the bonding characteristics of the adhesive. 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-Kpox, by contrast, not only reduces the viscosity of liquid epoxy resins by as much as 75 per cent but also speeds cure, reduces curing-agent 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 requirement, the incorporation of Mod-Epox generally lowers the for mulation cost greatly. Furthermore, MoivEpox is not a skin irritant like many other reactive diluents. Santicizer 8 Santicizlr 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 heatdistortion temperature. A major, new unique benefit of the use of Santicizlr 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 Santicizlr 8 should help to eliminate measuring errors and thereby reduce the fre quency of overcured or undcrcurcd batches of epoxy resins. \ 0t>0b5#3 TOWOLDMONOQ34146 '^S^^POLYESTER RESfNS '" ' "' ` ' - ' ' ' _' Fiberglass-reinforced polyester resins are widely used for the manufacture of industrial and con sumer 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. r * Although polyester resins are most often not plasticized, modification of their physical properties by plasticizers is desirable for some applications. Some of these modifications, and the appropri ate Monsanto plasticizers tharbest impart them, are as follows: Flame-retardance flexibility Resilience Moldability, gloss, and moisture resistance. Raster processing, clarity Initiator carriers (for easier, safer handling) Aroclor 1260, 4465, and 5460 Santicizek 100, Aroclor 1260, 4465, and 5460 Santicizer 160 Santicizek 9 Triphcnyl phosphite Dimethyl phthalatc, Dibutyl phthalate, Tricresyl phosphate, and Santicizek 160 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, riame-relardant combinations of equal quantities of an Aroci.or compound and antimony oxide act synergystically; the Aroclor compound imparls self-extinguishing properties to the resin, and antimony oxide reduces after-glow. The use of an Aroclor compound to impart flame retardance to a polyester 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-pcr cent con centration (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 poly ester docs. 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 Santicizek 160 as an external plasticizer in polyester resins increases flexibility and resilience (U. S. Patent Xo. 2,757,158, J. R. Darby and A. R. Hempcl, assigned to Monsanto Chemical Company). Cast sheet consisting of from 15 to 50 parts Santjcizek 160 per 100 parts unsaturaled polyester resin and 37.5 parts styrene is hard, tough, and resilient; whereas similar sheet without Santicizek 160 is hard and tough, but very brittle. 9 TOWOLDMON0034147 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--Trlphenyl Phosphite In the presence of a small amount of Monsanto triphenyl phosphite, the processing time of poly ester 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 AP11A 15 - 20 by the addition of 0.5-per cent triphenyl phosphite. Peroxide-Initiator Carriers Peroxide initiators ("catalysts") used in polyestcr-resin processing are more easily handled if diluted and desensitized by compatible plasticizers such as dimethyl phlhalate, dibutyl phthalate, tricresyl phosphate, and Santicizer 160. Polyester curing initiators are diluted with dimethyl phthalate, dibutyl phthalate, tricresyl phos phate, or SANTICIZER 160 for easier, safer handling. In polyester coatings, AROCLOR plasti cizers impart flame retardance. TOWOLDMONOQ34148 )} POLYAMIDE RESINS NYLON Plasticizers imparl belter low-temperature flexibility and improved impact resistance to nylon, increasingly important benefits since carbon black and other fillers tend to reduce these prop erties. Monsanto's sulfonamide plasticizers and resins--Santicizer 1-H, Santicizer 3, Santicizer 8, Santicizkr 9, Saniolitk MHP, and SaxtolitfMS-SO#--are useful as flexibilizers and modi fiers for nylon. Performance evaluations of five of these plasticizers are compared in the follow ing table: TABLE HI--EVALUATION OF PLASTICIZERS IN NYLON* Plasticiser (25 PHR) Stiffness et 770 F IH None (control) Santicizer 1-H Santicizer 3 Santicizer 8 Santicizer 9 Santolite MHP 35,900 11,560 10,850 12,700 9,800 5,790 *Du Pont's Zytrl 101 resin Hardness (Shore "O") 67 27 34 40 58" 28 ' Tensile Strength (p*'l 5700 3080 . 4930 1830 3100 3960 Elongation . (%) 320 100 480 250 350 360 a) 15 PHR Water Resistance Absorbed Solubles (%) Lost (%] 2.00 1.61 0.94 1.98 1.67" 1.24 0 0 0.16 1.89 1.30" 1.10 Santicizer l-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 imparls improved toughness, flexibility, and low-temperature flexibility to nylon with out affecting other resin properties. Santicizer S 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 concen- tl 05Udi>b6 TOWOLDMONOQ34149 tration of 20 per cent or less is usually sufficient for practical industrial uses. A patented com position* for precision casting, however, contains from 30- to 90-per,cent Sa.\ijcjzkn 9 with either nylon 6-6 or nylon 6-4. Such compositions, when cured, have a Rrineil hardness of S kg/sq mm (11,400 psi) and an impact strength of 8 to 10 kg/cni (45 to 56 lb/in.). Santoljte MHP ' . As a useful extender resin, Saniomte 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 hotmelt 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 applicaations, since they impart tack, increase flexibility, improve gloss, and lower the softening and heat-sealing temper atures. Several typical polyamide-based adhesives formulations are the following: POLYAMIDE ADHESIVES STARTING FORMULATIONS Ingredients Versawid 100 polyamide resin Verwroid 940 polyamide resin Santicizer 8 Santicizer 9 Aroclor 1254<* Dibutyl pbthalate Dicaprylhexyl phthafate Staybelite*** ester #10 Paraffin (m. 130eF) Candelilla wax Isopropanol Toluene Low-Tempe rafure 100 -- -- --. 12 -- 6 -- -- -- -- 100 -- -- -- 11 -- -- -- -- -- -- DelayedTack GeneralPurpose Hot-Melt (parts by weight) 100 -- 31.6-- -- -- -- -- 5.9 29.5 29.5 100 10b -- -- -- -- 10 ' 4 -- -- -- For Poly ethylene 100 100 16.6 -- -- 33.2 -- -- -- -- Bookbfndmg 100 -- -- 85 -- -- \ -- -- -- -- a) With a higher concentration of Santiciz.br 9, the tack may be delayed for several hours. b) Santicizer 8 increases the low-temperature flexibility c) U. S. Patent No. 2,612,465, assigned to the Du Pont Co. d) or Aroclor 1242, 1248, 1260, or 1262 German Patent No. 1,018,592, October 31, 1957, to Regie nationale des usines Renault Trademark of General Mills Corp. Trademark of Hercules Powder Co. 12 OSO8&07 i 0 TOWOLDMONOQ34150 PHENOL/C RESIGNSi MOLDING AND LAMINATING COMPOSITIONS Brake Bands and Clutch Faces Santjcizkk 9 is a valuable plasticizer and fluxing agent in the manufacture of molded phenolicresin 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 uniform ly. Usually comprising from 5 to 10 per cent of the composition, it greatly improves flexibility. Aroclor 1268 and Aroclor 2565 also improve flow properties and promote mixing and are useful in the manufacture of brake linings. Punching Laminates Several Monsanto plasticizers are often used to improve the cold-punching' characteristics of phenolic-resin laminates. Tricresyl phosphate and the Aroclor compounds also impart flame rctardance. Because of the sharpness of punches when tricresyl phosphate is used, at a concen tration of from 5 to 10 parts per hundred parts of resin, fewer finished parts are rejected. Tri cresyl phosphate also imparls some flexibility. The higher-molecular-weight Aroclor plasticizers (1262 and 5460) 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 Santicizlr 160 and dibutyl phthalate have good electrical prop erties, and at concentrations of from 5 to 10 PHR, they imparl suitable punching and flexing properties. Santicizkr 8 also imparls some flexibility, in addition to improving the cold-punching proper ties of phenolic laminates. HB-40 is also useful in electrical punching laminates. Composition Wallboard As a mixing aid, Santicizkr 9 is invaluable in promoting uniformity of phenolic composition wallboard. 13 TOWOLDMONOQ34151 ADHESIVES * Phenolic clutch- and brake-lining adhesives, containing Santicizer 9 at a concentration of about 10 PHR, have potential applications. In various phenolic hot-melt adhesives, Santicizer 9 im proves 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. 4 0508589 C TOWOLDMONOQ34152 MZMMMEjRESMS 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 fin ishes in baking or curing operations by improving flowou! and by minimizing pigment dis coloration. Santicizer 9 also increases impact strength and abrasion resistance and improves buffabilily 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. 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 diammoni um phosphate imparls flame retardance to melamine-urea-based intumescent coatings. Santolite MHP is a useful plasticizer and flow aid. In melamine laminates, SANTICIZER 9 produces higher-gloss finishes, improves buffability, and increases impact strength and abrasion resistance. 15 0508590 t6w6LdMON00341 53 SYNTHETIC RUBBERS ' ". CHLORINATED RUBBER x 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 rub ber-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 and food-processing plants; on railroad and marine equipment; and on high ways, for traffic markings. The Aroclor plasticizers primarily increase resistance to acids, alkalies, salt water, and mois ture; 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, di butyl phlhalate, triphenyl phosphate, tricresyl phosphate, and Santolite MHP. Aroclor plasticizers and dibutyl phthalate 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 ma sonry paints, aluminum coatings, wall scalers, 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 phos phate 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 coat ings that are commercially used on rubber products. . POLYBUTENE Mixtures of Aroclor plasticizers and polybutenes make permanently tacky coatings for fabric or paper. Such coatings are used for tape and sign backing, refrigerator-sealing compounds, auto-body and windshield mastics, and foundry-core seals. Coatings containing insecticides make effective insect traps or barriers on tree trunks for foliage or fruit protection. 16 0508591 TOWOLDMONOQ34154 4. / NITRILE RUBBER Plasticizers are essential to modify many characteristics of nitrile rubbers. They improve pro cessability, increase softness, reduce modulus of elongation, improve low-temperature proper* 1 tics, reduce volume change during immersion of vulcanizates, and lower the finished-product costs. .. Monomeric esters, such as dibutyl phthalate, 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: Plaiticixar Dibutyl phthalate Dioctyl phthalate Diisodecyl phthalate Santicizer 160 Santicizer 409 Santicizer All Compatibility (PHR) 100 50 55 100 50 50 ' ' Piastieizar Dioctyl adipate Diisodecyl adipate Tricresyl phosphate Santicizer HO Santicizer Ml Santicizer B-16 HB-AO . . Compatibility (PHR) 204 55 55 55 40 50 50 c) incompatible in higher-molccular-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 arc presented in Table V. Effects of aging (TableVI) and of solvent extraction (TablesVII 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 diisodecyl phthalate, dioctyl phthalate, and fIB-40. Santicizer 140, Santicizer B-16, tricresyl phosphate, Santicizer 160, and dibulyl phthalate is the leastefficient 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 hard ness increase for all plasticizers is less than the 15 points allowed. Slocks containing any of these plasticizers meet the B-suffix requirement under ASTM method D735-55T (35 per cent maximum). 0!>08*92 TOWOLDMONOQ34155 TABLE IV--PERFORMANCE OF PLASTICIZERS IN NITRILE RUBBER* Property Incorporation on Roll Mill (minutes) Mooney plasticity . Large rotor, 212*F Initial 1 minute 2 minutes . 3 minutes 4 minutes 5 minutes Compatibility (surface description: hung in air 36 days) Low'temoerature flexibility 5 hours, --40*F - 5 hours, --65*F Compression set, % Cure, 45 min., 310*F ASTM Method B. 70 hr., 212*F Dibutyl Phthelete 18 Dioctyl Phthalete 19 Diisedecyl SANTICIZER Phthalate 160 18 20 89 70 63 60 58 58 Dry 90 68 60 55 53 53 Dry 86 , 100 65 77 59 67 56 53 ' 62 58 52 57 . Dry Dry Flexible Stiff Flexible Stiff Flexible Stiff Flexible Stiff 27.? 30.6 30.6 27.9 ) Formulation: Ingredients Hycar* 1042 nitrile rubber Plasticizer FEF black Zinc oxide Stearic acid - Thiurad** activator Sul/dson** anti'aging compound cure: 20 min. at 310F Dioetyl Adipate 20 83 63 57 53 50 50 Very slight tack Flexible Flexible 27.9 Diisodecyl Adipate 19 Tricresyl SANTICIZER SANTICIZER Phosphate 140 141 16 18 IS HB-40 19 . 83 63 55 52 50 50 Very slight tack Flexible Flexible 94 72 65 61 59 58 Slight tack 98 80 * 75 67 62 ` 59 Very ' slight tack 98 71 62 58 56 54 / Dry 86 67 60 53 56 55 Very slight tack Flexible Stiff Flexible Stiff Flexible Stiff Flexible Stiff 28.8 27.2 Parts by Weight 100 15 50 5 1 0.8 0.8 27.2 26.5 29.2 Trademark of B. F. Goodrich Co. -' **Thiurad and Sulfasan are trademarks of Monsanto Chemical Co., registered in the U. S. Patent Office. 0508593 (! TOWOLDMONOQ34156 TABLE V-EFFECT OF PLASTICIZERS ON PHYSICAL PROPERTIES OF NITRILE RUBBER' Plasticizer (15 PHR) Dibutyl Phthalatc Dioctyl Phthalatc ` DirsodccyJ Phthalatc Santicizer 160 Dioctyl Adipate Diisodccyl Adipate Tricrcsy.l Phosphate Santicizer 140 Santicizer 141 Santicizer B-16 HB-40 Modulus at 300% Elongation Cp*U. 1100 mo ino 1200 1030 970 1290 1240 1150 . 1260 1150 Modulus at 500% Elongation (p*n 2070 2100 2060 2265 2110 2070 2370 2280 2180 2280 2170 n) Formulation and curing: same as for Table IV Ultimata Tansila Strength (p*<l 2210 2220 2310 2400 2280 2280 2540 2420 2360 2400 .2320 i%) Elongation 570 560 590 565 565 595 600 560 575 575 575 Hardness (Shora "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 2120F) Plasticizer (15 PHR) Dibutyl Phthalatc Dioctyl Phthalatc D/isodecyJ Phthalatc Santicizer 160 Dioctyl Adipate Diisodccyl Adipate Tricresyl Phosphate Santicizer 140 Santicizer 141 Santicizer B'16 HB-40 Modulus et 300% Elongation Ml 2040 1850 1760 1870 1870 1770 1910 1920 1790 2030 2040 . a) Formulation and curing: same as for Tabic IV Ultimate Tensile Strength fp*IJ . 2930 2770 2700 2830 2780' 2675 2890 2710 2850 2700 2910 \ Elongation 1%) 435 450 450 450 445 455 460 415 455 450 420 Hardness (Shora "A"] 67 61 60 63 60 59 62 64 62 63 68 0508594 TOWOLDMONOQ34157 TABLE Vlt--EFFECT OF PLASTICIZERS ON OIL RESISTANCE OF NITRILE RUBBER(After immersion in # I ASTM Oil for 70 hours at 212*F] Plasticizer (IS PHR) Modulus at 300% Elongation (p*'l Modulus At 500% Elongation (p*0 Dibutyl Phthalate Dioctyl Phthalate Diisodccyl Phthalate Santicizer 160 Dioctyl Adipate Diisodccyl Adipate Tricrcsyl Phosphate Santicizer M0 Santicizer Ml Santicizer B'16 HB-40 1630 1540 1630 1730 1580 1520 1760 1725 1680 1720 1560 -- 2820 2750 2860 -- 2725 2860 2860 2890 2740 2780 Ultimate Tonslie Strength Ip*') 2775 2900 2750 2860 2725 2725 2860 2860 2950 2740 2780 a) Formulation and curing: 6ame as for Table IV Elongation (%) 495 530 500 500 480 500 500 500 515 500 500 ' Hardness (Shore "A") Volume Change 1%) 55 --7.0 55 ` --7.0 55 --6.9 55 --5.8 58 --7.3 58 --6.8 58 --4.6 55 --5.1 55 --5.8 58 --6.1 59 --7.4 TABLE VIII--EFFECT OF PLASTICIZERS ON OIL RESISTANCE OF NITRILE RUBBER(After Immersion in #3 ASTM oil for 70 hours at 212*F) PlasticiiAr (IS PHR) Modulus at 300% Elongation (p*U Modulus at 500% Elongation (p*i) Dibutyl Phthalate Dioctyl Phthalate Diisodecyl Phthalate Santicizer 160 Dioctyl Adipate Diisodecyl Adipate Tricrcsyl Phosphate Santicizer 140 Santicizer 141 Santicizer B'16 HB-40 1210 1250 1230 1370 1200 1140 1420 1250 1320 1370 1220 2320 2350 2360 2500 2370 2370 2620 2530 - 2480 2520 2360 a) Formulation and curing: tame as for Table IV Ultimate Tensile Strength Ip*') 2550 2490 2430 2500 2460 2510 2700 2640 2530 2570 2520 Elongation (%) Hardness (Shore "A") 555 46 535 46 520 46 500 46 515 46 ' 535 46 510 49 540 46 510 46 515 48 535 48 Volume Change (%) + 7.5 +6.5 +7.2 + 8.3 + 7.2 + 7.0 +9.0 + 8.7 +8.5 + 7.5 +7.4 20 0508595 TOWOLDMONOQ34158 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 wcatherability (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-re sistant surfaces on bridges and highways. Liquid Aroclor compounds, such as Aroclor 1232, are excellent viscosity--and cost-reducing modifiers, at concentrations 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, solvent-resistant gaskets, and similar cast products. Either dibutyl phlhalate or an Aroclor plasticizer may be used at a concentration of about 40 PHR to modify polysulfide casting compounds. Liquid Aroclor compounds 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-40, 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. CREPE RUBBER (NATURAL) . Aroclor 1262 is used as a low-cost plasticizer for crepe rubber in paint compositions. In con centrations of from 5 to 50 per cent of the weight of the rubber, the Aroclor plasticizer in creases alkali resistance, gloss, and adhesivity to steel. Trademark of Thiokol Chemical Co. 21 0b06b96 TOWOLDMONOQ34159 tyP0LYVINYL/DENE CHLORIDE Vinylidcnc 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 coalings 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) arc very efficient. So arc Santicizer 141, Santjcizer 160, dioctyl phlhalate, and diethyl phthalatc. Performance of several plasticizers in sarart resin (vinylidene chloride-vinyl chloride copoly mers) are shown in the following table. TABLE IX --EVALUATION OF PLASTICIZERS IN SARAN- Santicizer B-16 Dioctyl Phthalate Santicizer 160 Santicizer E-l 5 Santicizer 21 3 Relative Compatibility^ 5% Plailiciier 10% Plesliclier 00 03 l2 a0 4 4 Volatility (S7C, 2 hr.) Plasticher tost (%) 5% Plasticizer 6.1 10% Plasticizer 13.8 7.8 7,8 5.7 12.4 10.1 18.0 5.3 11.8 Solvency Rating Precipitation Temp. (C) Hot Solvent Hot Solvent Hot Solvent Non Solvent ------- 130 96 92 -- Aroceor 5460 50 Santicizer 141 8 1 o) Saran resin B-118. Dow Chemical Co. b) On a relative scale from 0 = no exudation to 10 = incompatible 4.6 0.7 -- - 7.1 10.7 Hot 69 Solvent Completely nontoxic Santicizer E-1S and Santicizer B-16 are excellent plasticizers for saran. In bol-mclt, extruded-paper coatings, they aid in heat sealing and impart improved low-tempera ture flexibility. In solvent-cast saran-resin solutions, plasticizers impart improved flexibility and aid in solvent release. Generally, only small percentages of the plasticizer are required to pro duce a high degree of softness and elongation. For example, films containing 25-per cent Santicizkr 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 arc essential to laydown oF continuous, pinhole-frec 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 both dioctyl phthalate and tricresyl phosphate. Plasticizers generally impart to vinylidene chloride latexes the same properties they impart to polyvinyl chloride resins. 0*00*97 TOWOLDMONOQ34160 Efficient Monsanto plasticizers aid in heat sealing and impart flexibility, softness, and elonga tion to polyvinyiidene 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 Dow Latex 744-B Santicizer HI emulsion0 Methoeel* (15 cp.) methyl cellulose e) Phase A Santicizer HI Oleic acid Phase B 28% Aqueous ammonia Water % Solids 50 50 5 Parts by Weight 50 5 1 46 Dry Wet (parts by weight) 100 200 18 56 0.6 1.2 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-watcr emulsion. Trademark of Dow Chemical Co. 23 0508598 TOWOLDMONOQ34161 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 Santicizer 141 Syton* 200 colloido! silica Parti by Weight (dry) 100 25 19 ' , Scrub-resistant intumcscent coatings for low-density fiber wallboard and acoustical tile are based on vinylidene chloride-vinyl chloride copolymer latexes. Santicizer 141 and dioctyl phthalale are the recommended plasticizers for such coalings. A suggested starting formula is as follows: 1NTUMESCENT COATING Ingredients | Parts by Weight (wet) Monoatnmonium phosphate Dicyandiamide Pcntaerythritol Titanium dioxide (rutile) Water . 300 53 120 65 235 II Dow Latex 744'B (50% 6olids) Methocel (50 cp) (5% solids) Santicizer !41 (or dioctyl phthalate)* $<mtomee* 85* Water* 200 13.5 33 5.8 27.5 a) The plasticiier is emulsified by adding the wetting agent to it and mixing vigorously while slowly adding the water. >. The solvating, plasticizing, or swelling action of liquid plasticizers on the polymer at room tem perature seriously reduces the mechanical stability of the latex. Solid plasticizers, such as di phenyl phthalale, triphcnyl 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. Syton and Santomerse are- Monsanto Chemical Company trademarks, registered in the U. S. Patent Office. 0508599 TOWOLDMONOQ34162 Polyvinylpyrrolidone is a water-soluble, film-forming resin that when- unmodified dries to form hard, clear, -transparent, glossy films. Compatible plasticizers may be added to alter hardness, to control tack or brittleness, and to decrease hygroscopicity. . Compatibility limits of several plasticizers in polyvinylpyrrolidone are as follows: Plasticfcer Compatibility (PHR) Dimethyl Phthalate Santicizer E-15 Santicizer HI Santolite MHP 100 100 33 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 vinylpvrrolidone-vinyl acetate copolymers. Some of the end uses are in pressure-sensitive adhesives, rewettable adhesives, hair-grooming agents, white shoe polishes, and antilarnish coalings. 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, pressuresensitive films. Such comjx>sitions 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: \ 25 0508600 TOWOLDMONOQ34163 FORMULATIONS FOR PRESSURE-SENSITIVE-ADHESIVE COATINGS Ingredients \ Vinylpyrrolidonc'vinyl acetate copolymer* Opciton* 440 PVC resin Vinylite" VYH11 PVC resin Diocty! phthalate Methyl ethyl ketone Toluene a) I'5J5, General Aniline Film Corp. Plastisol ' Organ: (parts by weight) too 100 300 -- - too 200 15 200 200 To improve flexibility and reduce hygroscopicity, dimethyl phthalate may be added to hair grooming formulations ()0- to 2$-per cent based on resin solids). The following formulations are typical: ' SUGGESTED HAIRGROOMING FORMULATIONS Ingredients ' Vinylpyrrolidonc'vinyl acetate copolymer* Dimethyl phthalate . . . Santjcizer E'IS Lanolin derivative Silicone fluid Isopropyl myristate Perfume Ethanol (absolute) Ethanol (95%) Propellant (difluorodichloromethane) a) E'755, General Aniline & Film Corp. b) Lanogrl 41, Robinson-Wagner Co. Wave Set 100 __ 5' 12.5 2- 5 95 -- 900 -- Women's Hair Spray (parts by weight) 100 2.5 --' 12.5* 6.25 '- 6.25 372 2000 . Men's Heir Dressing < 100 2.5 25* -- 500 25 1845 10,000 Opalon is a Monsanto Chemical Company trademark, registered in the U. S. Patent Office Trademark of Union Carbide Corp. 26 0508601 V TOWOLDMONOQ34164 7PROTEIN RESINS Protein materials such as casein, zein, ally! starch, and soya protein require special plasticizers. 7'he following Monsanto products are plasticizers for these materials: Primary . Santicizer J Santicizer 8 Santicizer 9 Santolite MHP Saniolite MS'80% Secondary Triphcnyl Phosphate Tricrcsyl Phosphate Dibutyl Phthalate Santicizer 160 Aroclor Compounds Santicizer B-16 CASEIN Casein is a conjugated phosphoprolein 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. Un modified casein can be dissolved in water in the presence of a suitable alkaline medium such as ammonia, morpholine, or 2-amino-2-mclhyl-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 for maldehyde without causing reversable gels. It 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 pow ders 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 com patible in molding compositions to at least 50 PHR. Santicizer 8 (at a concentration of 67 I'HR in an aqueous-ammonia solution of casein) provides excellent flexibility and scuff and grease resistance in grease-proof-paper coatings. Santicizer B-16 and Santoute MS-80% make satisfactory emulsions with casein. 27 OSQ&bOZ TOWOLDMONOQ34165 Zein, an aqucous-alcohol-soluble corn protein, is a high-molecular-weight polymer composed of amino-acid groups united by peptide linkages. Solutions of zein in organic solvents or aqueous systems arc 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 or ganic 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 the alkyl aryl sulfonates. Unlike other proteins zein is resistant to microbial attack. Films and coatings are tough, glossy, scuffproof, and grease resistant. Fibers have wool-like properties, high tensile strength, and not able 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, Santicizer 8, Santicizer 9--and sulfonamide-formal dehyde 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 particularly adaptable to use as label and overprint varnishes that are tough, glossy, and scuff resistant. Santicizer 3 is per haps the bcst plasticizer 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-melt ad hesives. Santicizer 8 improves flexibility, water resistance, gloss, and adhesion and is compatible to at least 50 PHR. In label varnishes it prevents curling of the label. Santolite MHP is compatible with zein and improves brilliance, adhesion, and moisture resis tance 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. . 28 050603 TOWOLDMONOQ34166 Santoijte MHP markedly reduces viscosity and gelling of solutions of zein in 80-per cent iso propanol-- 20-pcr 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, hardness, 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 mill ing. 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 pellet ized 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 allyl 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 Agricul ture) as a suitable plasticizer for an allyl starch emulsion in a preferred pH range of 8 to 11. A typical emulsion formulation is as follows: Ingredients Atlyl 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). 'Trademark of Rohm Haas Co. Trademark of the Du Pont Co. \ 29 0*08604 TOWOLDMONOQ34167 ASPHAL T AND SHELLAC ASPHALT \ The major benefits of Monsanto plasticizers in asphalt are to pro,vide adhesion, tack, and flame retardancy. Aroclor 5460, at a concentration of 30 per cent, makes asphalt caulking, roof-coating, and sounddeadcning-coating compositions self-extinguishing. It also imparts adhesion and quick tack. Aroclor 5460 and 11B-40 are used together with asphalt to make sealers for asphalt roads. Montar compounds are also used to provide flame retardance. The Montar products are com patible 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 4 contributes flame retardance at concentrations as low as 10 per cent with instan taneous flame-out above 30 per cent. Flames are "snuffed" by an intumescent layer that for ms on the surface of the mixture. Solutions of Montar 4 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 4: ' TABLE X--EFFECT OF MONTAR 4 ON ASPHALT FLAMMABILITY SHELLAC Concentration of Montar 4 (%) 0 10 20 30 50 67 * Flame-Out Time (seconds) 210 90 10-20 Instantaneous Instantaneous Instantaneous Santicizer 8 increases the flexibility and definitely softens shellac without impairing the ad-' hesion of the resin. Santicizer 9 and Santicizer B-16 are also useful, although less effective than Santicizer 8. . 30 0508605 ) TOWOLDMONOQ34168 PLASTICIZER COUNCiL~Zl 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 requirements to Monsanto's Plas ticizer Council. With no obligation, you will obtain prompt attention; concentrated, experienced thought; skilled laboratory experimentation; thorough evaluation; and an unprejudiced recom mendation. , . There are many sound reasons why it will pay you to consider Monsanto's Plasticizer Coun cil as an extension of your own technical facilities--as many major plastics processers regu larly 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 asloundingly rapid rate. Plastics are being tailored for more and more applications, and their performance requirements arc be coming 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 plasti cizers, 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' accumu lated experience and data. And their new-product and product-improvement investigations are conducted in an environment 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 process ing 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 Chemical Company Plasticizer Council, Dept. PL-332 Organic Chemicals Division 800 North Lindbergh Boulevard St. Louis 66, Missouri 31 0>0#606 TOWOLDMONOQ34169 TECHNICAL BULLETINS ON , MONSANTO PLASTICIZERS Detailed technical information about the properties and applications of the Monsanto plastici zers 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 informa tion possible. We will promptly and cheerfully send you any bulletins you request. Technical Bulletin No. Sulfonamides PL-1'H PM PL-8 PL-9 PL-3 20 PMhatyl Glycolate Esters PL-15 PL-16 PL-17 Phosphate Esters PL-305 PL-501 PL-MO PL-141 Phthalate Eitert PL-50 2 PL-512 PL-505 PL-500 PL-518 PL-519 PL-160 PL-165 PL-215 Adipate Eitert PL* 308 PL-304 Other Plasticizers' PL-409 PL-411-D PL-315 PL-40 PL-317 PL-328 PL-306 PL-311 08-14 * .% (Chemical Specialties Data Report) General PL-307 PL-327 PL-331 Reprint- aeh-sm. 4/at 32 Title Santicizer 1-H Santicizer 3 Santicizer 8 Santicizer 9 SaNTOUte MHP and Santoute MS-80% ' Santicizer E-15 Santicizer B-16 Santicizer M-17 " Tricresyl Phosphate Triphenyl Phosphate Santicizer MO Santicizer Ml Dibutyl Phthalate Dicyclohcxyl Phthalate Diethyl Phthalate and Dimethyl Phthalate Diisodecy! Phthalate Dioctyl Phthalate Diphenyl Phthalate Santicizer 160 Santicizer 165 Santicizer 213 . Diisodccyl Adipate Dioctyt Adipate . Santicizer 409 Santicizer 411 Mod-Epox HB-40 Triphcnyl Phosphite ' Montar Compounds Aroci.or Plasticizers Aroclor resins and plasticizers for chlorinated rubber Aroclor Fire-Retardant Plasticizers and Modifiers for Epoxy Resins Monsanto Plasticizers in Synthctic-Rcsin Adhesives Monsanto Plasticizers in Protective Coatings Monsanto Modifiers for Thio^ol Polysulfide Liquid Polymers 0i00(,0t TOWOLDMONOQ34170 Q THESE REPLY CARDS ARE FOR YOUR CONVENIENCE Gentlemen:, (date) Gentlemen: (date) Please send me a copy of each indicated technical bulletin containing additional detailed information about Monsanto plasticizers for hard-to-p!asticize resins: o p t PL-_ < PL-_. PL-_ Pim plyPL-- s Comments.. cz o b. Name- Title_____ -1 Company. O Address.-- S City__ : sc State.. - o bJ K- -Zone____ Please send me a copy of each indicated technical bulletin containing additional detailed information about Monsanto plasticizers for hard-lo-plasticize resins: PL-. PL-. PL-PL-. PL-_ PL-_ Comments- NameTitle.. CompanyAddress.-- City______ State.. ___ Zone. mi < z 0 p 5 Gentlemen: (date) ? Gentlemen: (date) Q < (9 Z 1, S t Please send me a copy of each indicated technical Please send me a copy of each indicated lechnica bulletin containing additional detailed information ; bulletin containing additional detailed informatioi about Monsanto plasticizers for hard-lo-plasticize about Monsanto plasticizers for hard-to-plastiriz. resins: ? resins: PJy PL-- PL -- PL- PL-_ PL-__.. PL-_ PL-_ ___ PL-_ ___ PL-_ PlyPL-.. Comments_____ 5 Comments.... o Name- Name- Title- Title__ Company____ j Company --..... Address______ j Address__--____ City.________ State...______ __ Zone. \ City-----------------J i Stale... ..Zone. 0308608 TOWOLDMONOQ34171 ,,` ~in" r O I rzb z : c o3- o Q > t =>" O Wi O s: a. i. Q O 2 j0 **i c2. tosr !0. g Oc z I 5 2 tfl oo <| Q o m r* > so <t> So ?o c *V "P wr >z $ CO 5 kl " H S o u3 oz . o " 5=- o s: o z on > Z C TO O s: eTl tn 8i oo OI Cm Z2 00 0. <, J5O, J0" 0> mO "O -O r> ttoo z5 IO " 00 C </ Z m ut </i m *TJ .1" < > P* FIRST CLASS Pwrolt No. 3216 ST. LOUIS. M O . ; ' .---------------------------------------------------------------------------------------------------------1 O2 lQ0> s o' o OO Ocz X5 QO jr > mO -O -o r> uwM> z-< 09 c l/t z m U) (/) > J O O iQ r> ^O Q> Mi To O oo oC im Z Q o> mO 03 c V) Z m V) c/ m "0 -< *o y trtoo >Z5 ki " > FIRST C A S S P .fm lt No. 3016 ST. LOUIS. M O . TOWOLDMONOQ34172