Document jyJMwVyM5VXDQXx1KarZBNj2Z

Q CONTENTS ' INTRODUCTION'................................................................................................................ 1 GUIDE TO MONSANTO PLASTICIZERS TOR HARD-TO-PLASTICIZE RESINS........................................................ 2 ACRVLIC RESINS ........................ 4 EPOXY RESINS.................................... 6 POLYESTER RESINS ...!............................................................... 9 POLYAMIDE RESINS .....................'................................ ..................... ...................................... 11 PHENOLIC RESINS .............:....................................................... ..................................... ........... 13 MELAMINE RESINS ........................................................................................................ IS SYNTHETIC RUBBERS !......................................... 16 POLYVINYLIDENE CHLORIDE................... 22 i. POLYVINYLPYRROLIDONE ....................................................................................................... 2S PROTEIN RESINS ........................ ;.................. ............................................................................. 27 ASPHALT AND SHELLAC ........................................................................................................... 30 PLASTICIZER COUNCIL.........................................................................................-................... 31 ii TECHNICAL BULLETINS ON MONSANTO PLASTICIZERS........................................... 32 ;i The information contained in this bufletin is. to our be:t Inowledge. true and accurate, but ell re commendations or suggestions ero made without guarantee, since the conditions of use ere beyond our control. The Monsanto Chemical Company disclaims any liability incurred in connection with tho use of these date or suggestions. Furthermore, nothing contained herein sheti be construed as a recommendation to use any product In conflict with existing patents covering any material or its uso. iipiiw wmWMWHU ot?> ""mi m TOWOLDMON0005015 WATER_PCB-00001525 i? INTRODUCTION --.3 '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 formulators 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-eighty 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 better plasticizer. '' For more detailed information, we will gladly send you Monsanto technical bulletins on indlcated 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. 0221326 TOWOLDMON0005016 WATER_PCB-00001526 m GUIDE TO MONSANTO PLASTICIZERS FOR HARD-TO-PLASTICIZE RESINS PiMclier Fhthalatei Jibutyi dicydohexyl dfcthyi diisotlteyl dimethyl dioctyl diphenyl SantiHzbr* 160 Santiciie?. 165 SantiIszer 21} Adipates diisodecyl diocty| Acrylic JPOT Polyester Polyamide dimer acid* nylon based Phenolic Melamine Chlor inated rubber stj lentBut iiene Neoprene X X- --X X X X XX X X XX X XX X XX Phosphates Tricresyl Triphtayl Sakti^izer 140 Santidizer 141 $lyco|tai XX XX XX X XXXX X X (1 Santiciier E-15 Santidizer B*16 SANTICIZER Kl-17 X XX X XX Sulfonamides SANTICIZER l'H Santidizer 3 Santi|osbr 8 SANTfCfEER 9 Santolite* MHP Santolitz WS'80% XX --T~ --T~ X XX X X XX X X X --X- XX XX Other . RF55* X MoD'fepox* Triphtnyl Phosphite X ------- X Montar* Aroclor* SantIciier 409 1221 1244 1241 1240 C440 1242 X 1240 444$ 1440 X 1241 $440 2S4S 1242 X X lui MM SANTICIZER 411 SANTICIZER, Santoute, HB*40, Wod-Epox, Montar, and Arocloa are Monsanto Chemical Company trademark*, registered In the U.S. Patent Office. TOWOLDMON0005017 WATER_PCB-00001527 X* mulct denote the plasticizers mentioned in this bulletin as being most generally useful ift the indicated resin. Since other plasticizers may be used for special applications, and since Monsanto ijj con stantly adding to its vast fund of knowledge about plastieizrr/resin systems, it is always a good i ask Monsanto's Plasticizer Council for advice on difficult or unusual plasticizer-formulation problems. Poly* Nitrtla blrtOM rubber Poly. su|flde Polyvinyl. Silicone Crepe Men* rubber rubber chloride ' Vinylpyrrolldone Vinyl Homo* Acetate polymer Copolymer Casein -Zeiis ' Soy* AHyl starch Shellac pull 'X "x ... x,,,, * , ~T~ X X' s? X X X X X X X XXkX X XXXX X X X "r~ X X XX XXX X XkXX X X X------ X XX X X XX XX -r~r- X --X------ X X "X X X ..... ibi X X X IM sue XX Xk X X XX TT X X x Xk X 4 "BJT TOWOLDMON0005018 WATER_PCB-00001528 ,C TOACRYLfC 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, cast ings, 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, furni ture, and shipping drums. ~ Poor idhestalty 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. .................. ...... --r - 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 Santicizer 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 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 volatiliza- In Monsanto's continuing research and development programs to produce ever-better plasticiz- _ er8, 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.) _________________ ______________________ _______ $ 0221331 TOWOLDMON0005019 WATER_PCB-00001529 : TABLE I-PLASTICIZER PERFORMANCE IN ACRTUC RESIN 1 - . (IOO'C.23 l.) light* Hast. Lost ftapatrabffityc Humhiffyd StsbSRy RKdeter ' . i%i (Solvent Crsw) SttbSBty (9bi NONE > ._____ equivalent 84 SAxncmx 160 Standard 44.0 (Std) Standard - Standard 78 (Std) Dimthyl Phthalate '+ 43.8 Diethyl Phthalate ++ 41.7 Dibutyl Phthalate Dioctyl Phthalate .. i ' . equivalent :_____ ____ 46.3 41.3 + _k Diisodccyl Phthabte - __-- 4.5 ` 4 Santiozer 163 SANTICIZERB'16 equivalent 49.7 __ __ _____ 67 Dicydohcxyl Phthalate - -- 29.0 ' __ m DCHP/SANTK32ER 160 (2/1) --- 30.0 80 DCHP/Samtiozer 160 (1/2) equivalent Tricresy! Phosphate SANTtazek 140 . ' -- __ 12.4 . 31.0 ++ -- _____ - 80 67 SANTtaiex 141 equivalent 45.2 __ 75 J Santiozer 409/$Atmcns* j 160(2/1) Santiozer 409/Santkszbr ' ---- 27.5 slight neg. eqoiraleot 160 (1/1) ' 71 SaNTIOZER 409/SANTK3ZER 160 (1/2) . ------- 36.3 slight neg. equivalent I ) Solvency compared to lint of Swncntii ICO in one'or more of three phatfcBed'lacqucr on tinplate taco toluene or application of second way*: 10a solvation, gel temperature of plastjcaer'iesin mixture or of lacquer coat over dried coat, or bod. plattkaed'hcqucf system, and viscosity of plasticised lacquers. ' d) Plasticised lacquer on primed'Steel panels immersed in distilled water . b) Values for volatility may also include advent loss because of poor at 40*C for 100 hours, then panels rated according to ASTM test D*714. solvent release. . e) Plutidzeddacquer films on glass panda rrnMt' in VtsdtrOiatttr* t) Comparison of observed cheeking after either 3'minute immccrioa of .for 123 hours, then gloss'measured (highest values arc best). ^Trademark of Adas Electric Devices Co. TOWOLDMON0005020 WATER_PCB-00001530 IS? ^^jMlsPOXY RESINS '. Epoxy resins generally are chemically resistant, flexible, tough, ami adhesive. Available as solids, liquids, or solutions, they are useful in surface coatings, including chcmical-rcsistant coalings, maintenance coatings, baking finishes, and laminates; in adhesives; and in encapsulation, pot ting, lamination, and casting compounds. . Plasticizers are not ordinarily used in epoxy resins when maximum performance is desired. Be cause 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 1254, Aroclor 1260, or Aroclor 1262 imparts excellent chemical resistance, especially to acids and alkalies; flame retardanee; 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-Erox, 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, potting, 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. 1 Where additional softness or flexibility are desired, Santicizer 141 especially, Santicizer M-17, Santicizer B-16, Aroclor 1221, Santicizer E-15, dibutyl phthalatc, trlcresyl phosphate, San ticizer 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 ' ~- ; AROCIOR Plasticizers , * The Aroclor plasticizers are the most compatible of all the nonreaetive plasticizers evaluated. Like epoxy resins, they impart excellent chemical and oxidation resistance and improved adheslvlty. ilf J- .1 u ill!, om 133 c TOWOLDMON0005021 WATER_PCB-00001531 ,. TABLE II--PERFORMANCE OF MONSANTO PLASTICIZERS AND REACTIVE DOUBTS IN EPOXT RESINS PlesKeb*r-3 None (control) ' Dibutyl Phthalate SANTtCTXER E-15 . SANTtCdEIt M*17 Santictzer BI6 Tricrcsjrl phosphate SANTtCnFtt 140 SANTICfZER 141 Aroclor 1248 Aroclor 1221 Mod-Epox Santiozer 8 . : Vbeeefly* Baforo Adding - Altar Adding Caring Agnnt Cniny Ayrnt lep) . Up) 1 12.8004 7900 1550 , 1)00 5050 ; 2100 5150 . ; 2450 2300 . 2000 5750 ' 3000 -2850 . 2200 1500 . 1400 ' 7700 ; 43oo - 1650 | 1200 1650 . 1250 7600 3100 Physteel fapuBii Altar Cum (03 far @ I00*C) find Impact Resistance 0.2 -- -- -- -- -- -- -- 0.6 .-- 0.8-0.9 0.2 Clarity; fight Herdnem, refleeted Short-D** (%). . (10 sec) 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 10 10 6 7 15 22 5 40 '8 84 84 Physic*! Propsrfiai Altar Heat Aging (24 hoars @ 87*C in cctiwftd carbon) Heriinwc Shore "D" [10 ne] Weight Chance (%l ` 86 78 80 85 85 86 79 82 88 81 88 ` 88 --0.012 --0.7)4 0.119 --0.131 --0.013 -0.222 --0.284 --0.425 --0.682 --2.118 0.134 --0.007 ) Formulation ingndtmh Epoxy Rests ' Plasticizer Tctracthylenepenttatine Parts 100 25 8 6) AH are compatible in the liquid resin and in the cured resin; both at ro temperature tad after 0.5 hour at 100*C c) Brookfield LVF #4 spindle; 60 rpm unless otherwise specified d) 30 rpm 3 TOWOLDMON0005022 WATER_PCB-00001532 t . i. . ' ', Flammability and cost--two major limitations of epoxy resins--arc diminished through the use of AROCLor compounds: nonburning compositions arc made by the use of an Aroclor compound (1$ PHR) and antimony oxide (5 1*I1U). About one-fourth the cost of epoxy resins, ArocloK plasticisers permit significant cost reduction. ,. I - The use of the liquid Aroclor plasticizers (122! and 1248) fn aliphatic amine-cured epoxies 1 also improves flexural strength and comprcssive-yield strength, has little effect on tensile | strength, and only slightly lowers heat-distortion temperature and ultimate compressive strength, t They are commonly used in solvcntless coatings. ' | SoKd Aroclor compounds (1262 and 5460) greatly improve compressive strength, compressive- yield strength, flexural strength, and tensile strength; although they slightly lower the heat dls| tontion temperature. They are used, sometimes in combination with liquid Aroclor plasticizers, j ha solvent-containing coatings. ' | I j ' !' ! Extension of epoxy-resin adhesives with Aroclor 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. ,' JMod-Epox, 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 ill lowers the curing-agent requirement, the incorporation of Mod-Epox generally lowers the for mulation cost greatly. Furthermore, Mod-Epox is not a skin irritant like many other reactive diluents. - _ r Santicizer 8 ,* Santicizer 8 is another reactive diluent that effectively lowers the viscosity of epoxy resins and debases 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 polyaminc curing agent can be diluted in it for easier handling and more accurate metering. The use of solutions of curing gent In Santicizer 8 should help to eliminate measuring errors and thereby reduce the fre quency of overcured or undcrcurcd batches of epoxy resins. 8 0*1335 11 TOWOLDMON0005023 WATER_PCB-00001533 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 Faster processing, clarity Initiator carriers (for easier, safer handling) Aroclor 1260,4465, and 5460 Santicizer 160, Aroclor 1Z60,4465, and 5460 Santicizer 160 Santicizer 9 Triphenyl phosphite Dimethyl phlhalate, Dibutyl phthalate, Tricresyl phosphate, and Santicizer 160 MONSANTO PLASTICIZERS ................................. ' ' AltOCLOft Plasticizers ^ '` Hie 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 syncrgystically; 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 polyester resin offers the added advantage of eliminating the need for a higher-cost flexibiiizing 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 flexibiiizing poly ester does. At 20-per cent concentrations, each of these Aroclor compounds increases the impact Strength of the polyester resin, whereas the flexibiiizing polyester decreases it. Santicizer 160 The use of Santicizer 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 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. * o2*4rb TOWOLDMON0005024 WATER_PCB-00001534 Santicizer 9 Santicizer 9 improves processability of polyester molding compounds and also imparts gloss and moisture resistance to molded products, such as buttons. Catalyst/Clarlfier--Triphenyl 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 arc obtained. For example the processing time for a mateic 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-pcr 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. rr - __ _ . ' n:'*** . .Jr''........ . . Polyester curing Initiators are diluted with dimethyl phthalate, dibutyl phthalate, trlcreiyl pho phflte, or SANTICIZER 160 for easier, safer handling. In polyester coatings, AROCLOR plastj chars Impart ftama retardanee. \ 0221317 TOWOLDMON0005025 WATER_PCB-00001535 J1 i r i f. f' | I ($ i.. ! A 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 prop erties. Monsanto's sulfonamide plasticizers and resins--Santicizer 1-H, Sasticizer 3, Santicizer 8, Santicizer 9, Saxiolite MHF, and SantoliteMS-SO#--are useful as flexibilizers and modi fiers for nylon. Performance evaluations of five of these plasticizers are compared in the follow ing table: ' V TABLE III--EVALUATION OF PLASTICIZERS IN NYLON* Meitlelier * (23 PHR) Stiffness et77*F Ml None (control) SANtlClStR 1*H Santicizer 3 Santkjxea 8 Santicjxer9 Santolite MHP 35.900 11,560 10,850 ' 12,700 9,800 5,790 Du Font's Zytt\ 101 resin Herdnesi (Shore "D") 67 27 34 40 58* 28 Tensile Strength Ml Elongation m 3700 3080 .4930 1830 3100 3960 320 100 480 250 350 360 a) 15 PHR Wetor Resistance Abserbsd Solubles (%) Lost (%) 2.00 1.61 0.94 1.98 1.671.24 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 polfit. It imparts improved toughness, flexibility, and low-temperature flexibility to nylon with out affecting other resin properties. Santicizer 8 is excellent for oil-resistant nylon coatings on fabttcs and paper. Santicizer . . .. _____ 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 concern 1 022131 TOWOLDMON0005026 WATER_PCB-00001536 I tratipn 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-pcr.cent Sasticizer 9 with either nylon 6*6 or nylon 6*4, Such compositions, when cured, have a Hrinell hardness of S kg/sq mm <11,400 psi) and an impact strength of 8 to 10 Ug/cm (45 to 56 lb/in.). . ` SANTOUTS MHP V' .. As a useful extender resin, Santoute 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 adds 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 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 - Ingradiants . Vtrumid ** 100 polyamide resin VcrMtnld 940 polyamide resin SaktkXjebr 8 SANTICffcBR 9 A*ocloMJ34* Dibuty] phthalate Dkaprylhexyl phthalate Scaybeifte*0 ester #10 Puaffia <m. U0*F) Cendelilla wax Isoprophnol . .. Toluene Low-Tempera hra . 100 -- -- --. 12 -- 6 -- -- .-- -- * 100 -- -- -- 11 -- -- -- -- --* -- Oafayed- . Tack GeneralPurpose Hot-Mall (parts by weight) For Mlethylene too -- 11.0 -- -- 5.9 29.5 29.5 100 too --. . 10* 100 -- 16.6 --_ ---- _ 22.1 10 ' ' -- 4-- .-- -- ---- -- --- Soak binding1 _ 100 -- -- 85 -- -- \-- -- -- '-- -- <) With a higher concentration of Santictzcr 9, the tack may be delayed for several hours, b) SANjTicizea 8 increases the low*temperature flexibility e) U. 8. Patent No. 2,612,463, assigned to the Du Pont Co. 4) or AaOCLOR 1242, 1248, 1260, or 1262 . German Patent No. 1,016.592, October 21, 1957, Co Regie nationale del usines Renault Trademark of Genetal Mills Corp. Trademark of Hercules Powder Co. e TOWOLDMON0005027 WATER_PCB-00001537 'PHENOLIC WSMSZZJi MOLDING AND LAMINATING COMPOSITIONS . Brake Bands and Clutch Faces Santicizer 9 is a valuable plasticizer and fluxing agent in the manufacture 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 mien 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. Flinching 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 lelardance. 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 imparts some flexibility. The higher-molecular-weight Aroclor plasticizers (1262 and 5460) arc often used for their flame rctardancy. 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 prop- ertles, and at concentrations of from 5 to 10 rHR, they impart suitable punching and flexing properties. - *- -- j Santicizer 8 also imparts 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, Santicizer 9 is invaluable in promoting uniformity of phenolic composition wallboard. 13 0221340 f TOWOLDMON0005028 WATER_PCB-00001538 1 i if i ft PhvnoSc-restn binders, plasticized with HB-40 or dibutyl phthalato, In foundry shell molds per- | mlt closer tolerances and smoother castings. | 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, Santicizex 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 i phenolic marine varnish that performed well in a 14-month Florida weather-exposure test,' ' AaoCLQK 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 SANTicuan 9 improves flexibility and printabillty. 14 (T TOWOLDMON0005029 WATER_PCB-00001539 MELAMINE'RESINS "j laminates In melamine laminates, Santicizer 9 improves flow characteristics,. imparts greater solutionj stability, and permits drying to lower moisture content. Santicizer 9 produces higher-gloss fin ishes in baking or curing operations by Improving flowoul and by minimizing pigment dis-J coloration. Santicizer 9 also' increases impact strength and abrasion resistance and Improvi buffability of the finished coating or laminate. HlGH-IMPACT MOLDING COMPOUNDS Santicizer 9 improves dimensional stability and reduces warpage, the two major problems o( 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 develog ment of some of the internal stresses. INTUMESCENT. FIRE-RETARDANT COATINGS A combination of either Santicizer 140 or tricresyl phosphate with either mono- or diammohij um phosphate imparts flame retardance to melamine-urea-based intumescent coatings. Sani LITE MHP is a useful plasticizer and flow aid. L_/5 Jii ||n molamtne laminates, SANTICIZER 9 produces higher-gloss finishes, Improves buffability, Ineroases Impact strength and abrasion resistance. Mb 0221342 SfSfP mm TOWOLDMON0005030 WATER_PCB-00001540 t i i , j I ' 3 * m I' tf ' ' SH^-ilbSYNTHEtiC RUBBERS' ............. CHLORINATED rubber ' . . 1 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 nib . 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. I The Aroclor plasticizers primarily increase resistance to acids, alkalies, salt water, and mots- ture; but they also impart adhesivity, improve. cold-check resistance and weathcrabllity, and ( make softer films. }' | , j Othfr Monsanto plasticizers useful in cbtorin&ted-rubbcr coatings include Santicizer B-16, dl- butyl phthalate, triphenyl phosphate, tricresyl phosphate, and Santolite MHP. ' Asocto* 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 . j Styrene-butadlone copolymers are widely used in enamels, maintenance finishes, exterior ma1 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. 4 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, i Neoprene modified with Aroclor compounds Is very useful as wire and cable coatings. Aroclor | $460 Imparts plasticization and adhesivity to neoprene-based protective and decorative coat- i logs that are commercially used on rubber products. . t. 1 | | j ! ! | * POLYBUTENE . ' Mixtures of Aroclor plasticisers 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. 14 . .. . . 02*vV> k t V</1 TOWOLDMON0005031 WATER_PCB-00001541 NITRILE RUBBER Plasticisers ate essential to modify many characteristics of nitrile rubbers. They improve pn cessability, increase softness, reduce modulus of elongation, improve low-temperature plrope - t(ts, reduce volume change during immersion of vulcaniiates, and lower the finished-produt t costs. .. .Monomeric esters, such as dibutyl phthaiate, dloctyi phthalate, and dioctyl adipate are goo I softeners, have pleasant odors, and impart improved low-temperature properties. Polyester such as Santicuer 409'and Santicuer 411, impart good physical properties, low volatUlt] and resistance to extraction by oils and solvents. ' Compatibilities of common plasticisers in nitrile rubbers are as follows: Hastictiar Dibutyl phthalate Dioctyl phthalate Diisodecyl phthalate Santicuer 160 Santicuer 409 ' Santicizer 411 Compatibility [9HRJ 100 50 33 100 50 50 ' ' Hattiebar Dioetyl adipate Diisodecyl adipate Tricresyl phosphate Santicizer HO Santicuer HI ` Santicizer B*16 . HB-40 . . Compatibility . t^HRJ 30* IS 33 33 40 50 50 a) ineompstfble 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 arc presented it , .Table V. Effects of aging (Table VI) and of solvent extraction (TablesVII and VIII) on these 1 '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 HB-40. Santicizeii 140, Santicuer B-16, tricresy! phosphate, Santicizer 160, and dibutyl phthalate is the least' --efficient group of plasticizers. t.NWte of the plasticizers significantly affect either cure rate or tensile strength. The decrease inj ' elongation is much less than the 50 per cent allowed by AST.M method 735-55T, and the hard . ness increase for all plasticizers is less than the IS points allowed. Stocks containing any of these plasticizers meet the B-suffix requirement under ASThl method D735-S5T (35 per cent maximum). wmnmmmmmm *nf TOWOLDMON0005032 WATER_PCB-00001542 O tt y O' TABU IV--PStFORMANCEOFnASTICIZBtS IN NITRIU RU8BSf : KbutyI EBoeM DSsodeeyl Santiozbi Oteetyf DSserfecy! Triesusyl SAwnctzet SAMTtCtZES FW*Afu ftffmbf* PMfcuU* *80 AdlpatO Adtpm fliospfeoa 140 141 Incorporation on Roll MSI (minutes) Mooney plasticity . targe rotor, 212*F Initial 1 minute 2 minutes . 3 minutes 4 minutes 5 minutes Compatibility (surface description: bung in air 36 days) Lour-temperature flexibility 5 bouts, --40*F S boors, ---65*F Compression set, % Cute, 45 min, 310*P ASTM Method B. 70 hr, 212*F 18 89 70 63 60 58 58 Flexible Stiff 27.9 19 18 20 90 86 . too 68 65 . yj 60 59 67 55 56 62 53 ; 53 58 53 52 57 Dry . Dry Dry Flexible Stiff Flexible Stiff Flexible * Stiff 30.6 30.6 27.9 20 19 83 63 57 53 50 . 50 Very lligbt tack 83 63 55 52 50 50 Very slight tack Flexible Flexible Flexible Flexible 27.9 284 16 94 71 65 61 59 58 Slight tack Flexible Stiff 27.2 18 18 98 98 80 ` 71 75 62 67 58 62 * 56 59 54 ^ Very Dry Slight tack Flexible Stiff Flexible Stiff 27.2 26.5 a) Formulation: ItjftAnh Hycar* 1042 nitrile rubber Plasticizer FEF black Zinc oxide Stearic add - Thiurad** activator SulfoMn** anti-aging compound cure: 20 min. at 310*F Part* by WtlfM 100 IS SO s 1 04 04 "Trademark of B. F. Goodrich Co. **Thted and SkI/mm are trademarks of Monsanto Chemical Co, registered in the U. S. Pateat Office. HMD 19 86 67 60 58 56 55 Very slight tack Flexible Stiff 29.2 e TOWOLDMON0005033 WATER_PCB-00001543 $ I i. i 1 I i I $ TABLE V--EFFECT OF PLASTICIZERS ON PHYSICAL PROPERTIES OF NITRILE RUBBER* Plattlefar (l PHR| Dibutyl Phthalate Dioctyl Phthalate ' DiUodecyl Phthalate Bamucizer 160 Dioctyt Adipate Diliodecyl Adipate Tricmy] Phosphate Sanucizer mo Sahticizbr Ml SANTfCtlEK B*16 HB*40 Modulus at 00% Elongation M. 1100 mo 1*70 1200 10*0 970 1290 1240 1150 . 1260 1150 Modulus #1 600% Elongation (p<*) 2070 2109 2060 2265 2110 2070 2270 2280 2180 2280 2170 a) formulation and curing: ranters for Table IV Ultimata Tensile Strength (P*I) M10 2220 2*10 2400 2280 2280 2540 2420 2*60 2400 .2*20 i%i Elongation ^ 570 560 590 565 565 595 600 560 575 575 575 Herdnen (Short "A") 54 54 55 52 52 57 57 56 56 56 TABLE VI-EFFECT OF PLASTICIZERS ON ASIN OF NITRILE RUBBER* (After aging for 70 Kotin at 212*F} ,, - Pleitteher (IS PHR) Dibutyl Phthalate Diocty! Phthalate Diirodecy] Phthalate Sahticizbr 160 Dioctyl Adipate ..- Diiaodccyl Adipate Trietwyl Phoiphate SaNIricreEK HO Santicizer Ml 8ANHCiZRR&'16 ' HD-40 . " ; Modulut at 200% Elongation (fM 2040 1850 1760 1870 1870 1770 _ 1910 1920 1790 20)0 2040 . ) Formulation and curing: same at for Table IV Ultimato Tansllo Strangth (pu . 29*0 2770 2700 28)0 2780* 2675 ' 2890 2710 2850 2700 2910 \ Elongation i%) 425 450 450 450 445 455 460 415 455 450 420 Hardnoi* (Short "A") *7 61 60 A* 60 59 41 64 62 6* .. 68 ^ppijppyi ijLnii iijnijf'u.wfi.||i| w'wiuw)# TOWOLDMON0005034 WATER_PCB-00001544 TABLE VII--EFFECT OF PLASTICIZERS ON OIL RESISTANCE OF NITRILE RUBBER* (After immersion in # 1 ASTM Oil for 70 hours at 212*F] Plasticiser 1U PHRJ Dibutyl Phthalate Dioctyl Phthilate Diiiodccyl Phthalate SaNTICIZER 160 Dioctyl Adipate Diiiodccyl Adipate Tricreiyl Phosphate SaNTICIZER 140 Bahtiohr 141 Bantiozer B>16 HB'40 Modulus ot *00% Elongation fpell 1630 1540 1630 1730 1580 1530 1760 1715' 1680 1730 1560 Modulus ot 800% Elongation (pal) '--- 2820 2750 2860 -- 2725 2860 2860 2890 2740 . 2780 Ultimata Tensile * Strength Ipiil 2773 2900 2730 2860 2725 2725 2860 2860 2930 3740 2780 e) Formulation and curing: same at for Tabic IV Elongation (%) 495 530 500 500 480 500 500 500 515 500 500 Hardness (Shore "A") 53 35 55 55 58 58 58 55 55 58 39 Votuma Change (%) --7.0 ' --7.0 --6.9 --3.8 --7.8 -61 --4.6 --5.1 --3.8 --6.1 --7.4 TABLE Vlll-EFFECT OF PLASTICIZERS ON OIL RESISTANCE OF NITRILE RUBBER* (After Immersion in #3 ASTM oil for 70 hours at 2I2*F) PUstletsur (18 PHRJ Modulus at 200% Elongation Modulus at 800% Elongation Dibutyl Phtliilate Diocty] Phthilate Diiaodeeyl Phthalate SANTtcnea 160 Dioctyl Adipate Diiaodeeyl Adipate Tricreiyl Phosphate Santicizbr 140 SANTICfZjEB 141 BANTKtZER B*16 HB'40 1210 1230 1230 1270 1200 1140 1420 1250 1220 1370 1220 2320 1350 2360 2500 2370 2370 2620 2530 ' 2480 . 2520 2360 #) Formulation and curing: aamc aa for Tabic IV Ultimata Tensile Strength (p*!| 2550 2490 2430 3500 2460 2510 2700 . 2640 2530 2570 .2520 Elongation (%) 555 335 520 500 515 * 535 510 540 510 315 535 Hardness (Shorn "A") 44 . ` 46 ' 46 46 46 . 46 . 49 46 46 48 48 Velum. Ch.ng (%) +7.5 +4.5 +7.2 +*. +7.1 +7.0 +0 +5.7 +.5 +7.5 +7.4 20 &/ TOWOLDMON0005035 WATER_PCB-00001545 ;I W <i li II i! i POLYSULFIDE RUBBERS Thiokol* polysulfide liquid polymers are easily converted "in place".to rubbery materials.! Cured polysutfide rubbers are noted for outstanding oil and solvent resistance, excellent weath* erability (oxygen, ozone, and light), good electrical insulation properties, resilience, and broad leiVice-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 tosts. , 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-realstant 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 . 1 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 phthalate 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 , b 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 eoncentratlons 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 Thioko! Chemical Co. 2 0221344 m WWWPWW -! PWW.JHJ4WI Mliiaw TOWOLDMON0005036 WATEFLPCB-00001546 YVINYLIDENE CHLORIDE & `I Vinylidene chloride homopolvmers and copolymers have excellent chemical resistance and low ji 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 glvcolates (Santicizer B-16, Santicizer E*15,and Santicizer M-17) ' are very efficient. So are Santicizer 141, Santicizer 160, dioctyl phthal&te, and diethyl phtha> late. Performance of several plasticizers in saran resin (vinylidene chloride-vinyl chloride copoly men) are shown in the following table. TABLE IX -EVALUATION OF PLASTICIZERS IN SARAN- Santiciiba B-16 DJoctyl PhtHaktc SANTICnW 160 SANTICttH B'15 SanticizhIII Rotative Competibliltyt *% Pleitielter 10% PUitictsor 00 0' s I2 1 0 '4 4 * Volatility |W*Cv,. 24 hnr.)f PUiticiier loit (%) % Ptetticber 10% Pleiticber 6.1 15.8 7.8 7.8 5.7 12.4 10.1 18.0 5.5 11.8 Solvency Rating Precipitation Temp. (*C) Hoc Solvent Hoe Solvent Hot Solvent Hon* Solvent ----- r 150 96 92 -- -- Aaocloa 5460 I 0 . 4.6 0.7 -- - SANTjazU 141 ' 8 '' 7 a) Saran terin B'llS, Dow Chemical Co. b) On a itiative Kale from 0 = no exudation ` -- ...... to 10 S2 incompatible 10.7 Hot Solvent 69 * 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-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 Santi cizer B-16 with saran F-120 resin have greater than 300-per cent elongation. * Vinylidene chloride latexes, such as Dow latex 744-B arc used in paper coatings..Plasticizers are essential to laydown of- continuous, pinhole-free films. Plasticizers that accelerate fusion of latex, particles aid in giving a pinhole-free coating. Strongly solvating plasticizers aid in heat Mating. Santicizer 141 is excellent in these respects and is superior to both dioctyl phtbalate and trlcresyl phosphate. Plasticizers generally impart to vinylidene chloride latexes the same properties they impart to polyvinyl chloride resins. > 0 02213V I TOWOLDMON0005037 WATER_PCB-00001547 (0 i - * ---------------- a-7!."r-\----------------------------------------------------- >" ' >* ;f A i *.>' r ; ' . . *<.>' *' t Jf. . ' \. ` . >/ ;' ' ""*?/*>'I.( __ vifcv &*&.. i-*h J" " /v. * s. -V/ Vv^ / / V.'.w I'Tana* !t BBSS Efficient Moment plasticizers aid In heat sealing and Impart flexibility, softness, and longajtipn to polyvinylidene chloride barrier coatings on packaging films. A starting point for a clear coating for paperboard containers is as follows: CLEAR COATING FOR PAPERBOARD CARTONS Isigredfsnls Dow Latex 744B Santiciiex 141 emulsion* Methocel* (15 cp.) methyl cellulose a) Pbata A Santickes 141 Oleic add . % Solids 50 50 5 Ports by Weight 50 3 iy Wot (parts by sight] 100 300 13 36 0.6 U . Phase B ' 38% Aqueous ammonia Water I . 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. "Trademark of Dow Chemical Co. iiiiaaegwswy.1!! 022X350 TOWOLDMON0005038 WATER PCB-00001548 A dear wallpaper coating can be produced with Sasticixew 141 added without emulsification. A starting formulation is: * CLEAR, WASHABLE WALLPAPER COATING Ingredients Dow Latex 744 B $AMTiateal41 SytOH* 200 coHoidol silica ' lerts by Weight (dry) 100 23 19 Scrub-resistant intumescent coatings for low-density fiber wnllboard and acoustical tile ate based on vinylidene chloride-vinyl chloride copolymer latexes. Santicuer 141 and dioctyl phthal&te are the recommended plasticisers for such coatings. A suggested starting formula is as follows: Ingredients INTUMESCENT COATING Parts by Weight (wet) Monoammonium phosphate Dicyand(amide Pentaerythritol - Titanium dioxide (rutfle) * Water *' . 100 31 120 5 233 t*n tl . Dow Latex 744*B (50% colids) Methocel (50 ep) (5% solids) . Saktickbr 141 (or dioctyl phthUte) Sentomem* S3* Water* 200 1S.5 II 5.8 27.3 ) The plctticittr s* emulsified by adding the wetting agent to it and mixing vigorously while slowly adding the water. . The solvating, plasticising, 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 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 Xo. 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. dyten and Santemem ere- Monssnto Chemical Company trademarks, registered in the U. 8. Patent Office. 24 oil TOWOLDMON0005039 WATEFLPCB-00001549 9 POLYVINYLPYRROLIDONE J Polyvinylpyrrolidone is a water-soluble, film-forming resin that when- unmodified dries to form hard, dear, 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 polyvinytpyrrolidone are as follows: . tUitl.U.i . Compatibility (RHR) Dimethyl PhthaHte Santicizm E-l 5 $AtmctzEtt U1 Santolitz MHP ` 100 too 13 ' 11 . . Essentially tack-free films at any relative humidity arc obtained by the addition of 10-per cent Santolite MilP, Dimethyl phthalate functions at a relative humidity of as high as 70 per cent, whereas Saxticizer E-I5 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, rewritable adhesives, hair-grooming agents, white shoe polishes, and antitamish coalings. . Monsanto plasticizers compatible with vinylpyrrolidone-vinyl acetate copolymers include: ...... ... . ........ i- ' . _ dimethyl phthaiate dibutyl phthalate Saxticizer B-16 Santicizer E-l 5 Santicizer 141 Saxticizer 213 Santoute MHP ' . Generally 1:1 ratios of copolymer and compatible plasticizers yield adhesive, tacky, pressuresensitive 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: \ 25 TOWOLDMON0005040 WATER_PCB-00001550 FORMULATIONS FOR PRESSURE-SENSITIVE-ADHESIVE COATINGS Ingredients Vinylpyrroldone*vinyl acetate copolymer* Option* 440 PVC min. Vtuyltte** VYHH PVC min Dtocty! phthalate Methyl ethyl ketone Toluene a) 1*535, General Aniline 9 Film Corp. Pleslisot ' Organosol - (porta by weight) 100 100 too -r -- too 200 15 -- 200 200 To improve flexibility and reduce hygroscopicity, dimethyl phthalate may be added to hair grooming formulations (10- to 25-per cent based on resin solids). The following formulations are typical: ' SUGGESTED HAIRGROOMING FORMULATIONS Ingredients " .` Vinylpyrrolidone-vinyl acetate copolymer* Dimethyl phthalate . . . BANTiam E`13 Lanolin derivative Silicone fluid leopropyl myrutate Perfume Ethanol (absolute) Ethanol (93%) Propellant (difluoroJichloromethane) ) B*7I5, General Aniline 9 Film Corp. ) Lsnogei 41, Robinson-Wagner Co. Wove Sot 100 -- 5*12.3 2* 5 . *-- . 95 -- 900 -- ' ' ' Women's Heir Spray (parts by weight) 100 15 --* 12.5* 6.23 `-- . 6.25 172 -- . 2000 Men's Hair Dressing t 100 2.5 -- 25b -- 500 25 1845 -- 10,000 , '` . Opoloif li a Monsanto Chemical Company trademark, registered In the U. S. Patent Office Trademark of Union Carbide Corp. 26 0 TOWOLDMON0005041 WATER_PCB-00001551 PROTEIN RESINS 1 Protein materials such as casein, zein, allyl starch, and soya protein require special plasticisers. The following Monsanto produets are plasticisers for these materials: Primary . Santicizer ) Santicizer S - Santicizer 9 , Santomtb MHP Santoute MS'80% {waJtry * Triphenyl Phosphate Tricreayl Phosphate Dibutyl Phthaiate Santicizer 160 . Aroclor Compound* Santicizer B>16 CASEIN * Casein is a conjugated phosphoprotcin obtained from milk. Its use in surface coatings has'been j 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 j In water; formaldehyde is added to form a film that, when dry, is fairly water resistant. Un- j modified casein can be dissolved in water in the presence of a suitable alkaline medium such as ammonia, morpholine, or 2-amino-2-methyM-propanol. Hie 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. j 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 ctnt), and water (10 per cent) are compression molded into buttons. I j Santicizer 8 In casein improves flexibility, Water resistance, gloss, and adhesion and is compatlble In molding compositions to at least SO 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 Santolvte MS-80% make satisfactory emulsions with casein. I 27 0 UV** TOWOLDMON0005042 WATER_PCB-00001552 ZEIN Zein, an aqueous-alcohol-soluble com 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 slde'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, Kuffproof, 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-fonnal- dehyde resins--Santoute MHP and Santoute MS-8001--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 aa label and overprint varnishes that are tough, glossy, and scuff resistant. Santicizer 3 is per- hips thp best plasticizer available for zein, in which it is highly compatible. Formulations plas ticized with Santicizer 3, sometimes in combination with Santoute MHP or rosin derivatives, are useful as decorative lacquers, release coatings for pressure-sensitive tapes, and hot-melt ad- heslves. . .. . . Santicizer 8 improves flexibility, water resistance, gloss, and adhesion and is compatible to at hast 50 PHR. In label varnishes it prevents curling of the label. Santoute MHP is compatible with zein and improves brilliance, adhesion, and moisture resis tance of zein compositions. The incorporation of Santoute MHP in protein compositions makes possible the use ol plasticizers that are otherwise incompatible. Thus, fairly flexible compositions can.be formed by the use of Santoute MHP, plus Santicizer B-16 equal to about half the weight of Santoute MHP, . . M '' ' i pwi.ni li'n.liiiiJti'WS'iiiPsiRwjriieiawisiqiJIltgjtlltllglj.iiii ..I.i.iu.lllftjliJ|1J . i, 0221355 TOWOLDMON0005043 WATER_PCB-00001553 Santomte MHP markedly reduces viscosity and gelling of solutions of 2ein in 80-per cent iso propanol--20-per cent toluene. It also improves water resistance of cast zein films. Highly grease-resistant and grease-proof zein-based coalings 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 Santicuer 8 or Saxticizer 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 coatingsolmtons. 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 altyl 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 ally! starch in furniture finishes and grease-proof paper. The AROClor compounds are highly compatible and very efficient plasticizers for ally] starch. . Aroceor 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: ,, ' IngriditnH . 'AM Surch -W.-.AMW1.0R, 1242 - - lWn*X-10O . - Ammonium Hydroxide (cone.) Water , . Part* by Wofght - -------- 100 15 ' 4,25 4 210 . .. .................... . ' . ' .. . The emulsion is stabilized by addition of sodium tetrahydronaphthalene sulfonate (AlJtawt** S). _ *Tdem#rk of Rohm V Hm Co. ^Trademark of che Du Pont Co. . \ 29 022139 TOWOLDMON0005044 WATER_PCB-00001554 ASPHALT AND SHELLAC " ASPHALT \ . The major benefits of Monsanto plasticizers in asphalt are to provide adhesion, tack, and flame retardancy. . Axoclok 5460, at a concentration of 50 per cent, makes asphalt caulking, roof-coating, and sounddeadcning-coaling compositions self-extinguishing. It also imparts adhesion and quick tack. Axoclox 5460 and HB-40 are used together with asphalt to make sealers for asphalt roads. Montax 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 Montax compound is Increased. Blending is accomplished by thorough mixing, with heat if necessary. Montax 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 Montax 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 Montax 4: ' - .. TABLE X--EFFECT OF MONTAR 4 ON ASPHALT FLAMMABILITY . . - - SHELLAC Concentration of Montar 4 no 0 10 20 30 50 67 -. . . . Flame-Out - (seconds) :. . `: 210 90 10-20 ' . Instantaneous Instantaneous Instantaneous " '................- - - SANTtcieEx 8 increases the flexibility and definitely softens shellac without Impairing the ad- ' besion of the resin. Santicizek 9 and Santicizex B-16 are also useful, although less effective than Santicizex 8. . 30 npppswgMpnnBfifip^ 022X3*1 TOWOLDMON0005045 WATER_PCB-00001555 PLASTICIZER COUNCIL Perhaps your toughest, most urgent problem is not mentioned in this bulletin. Or maybe 4he suggested solutions do not completely meet your specific requirements. It may prove worth your while to present your problem and requirements to Monsanto's Pjias- tidier Council. With no obligation, you will obtain prompt attention; concentrated, experienrr|ei d thought; skilled laboratory experimentation; thorough evaluation; and an unprejudiced rec^i mendatlon. " ' There are many sound reasons why it will pay you to consider Monsanto's Plasticiser Co indl as an extension of your own technical facilities--as many major plastics processers re, it* larly do. As the pioneer in the art, technology, and science of plasticizing, Monsanto is unlqu ify organized to develop and capitalize on & team of research experts in all aspects and phases of plasticizer performance. * Since Monsanto produces more different plasticizers and' more different classes of ptastictu than any other company anywhere, the Plasticizer Council can (and always does) suggest t lie One best plasticizer system to meet your performance and cost requirements. You never ne d to worry about Monsanto promoting a particular plasticizer just because it happens to bc[* Monsanto specialty. Your best interests always govern our proposals. As you well know, new resins are being developed at an astoundingly rapid rate. Plastics being tailored for more and more applications, and their performance requirements are coming tougher. Just as you keep ahead in your major areas of technical competence, 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 plastj elms, Including new* products, product and process improvement, and customer service, worl to your definite advantage. Chemists working on your problem can bring to bear the lat< research results and thinking, as necessary, as well as drawing on more than 30-ycars' accumt lalcd experience and data. And their new-product and product-improvement investigations ar conducted In an environment of keen awareness of and appreciation for practical induslrh 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. Foij 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. Louts 66, Missouri . . ozzim TOWOLDMON0005046 WATER_PCB-00001556 TECHNICAL BULLETINS ON MONSANTO PLASTICIZERS Detailed technical information about the properties and applications of the Monsanto plastici sers mentioned in this bulletin is included in the following Monsanto technical bulletins. We revise these bulletins as often as nc$essary to include the most up-to-date and reliable informa tion possible. We will promptly and cheerfully send you any bulletins you request. Tsetmleal Bulletin No. Sulfonamides PL-l-H PI/) PL'S PL-9 PL->20 Phtfalyl Glyeolate Esters PL-15 PL-16 PL-17 Photphete Eiton PL-SOS . PI/101 PL-MO PL-141 ' PKfKalat* Eiters PL-101 . PL-112 PL-10) PL-100 PL-IIS PL-SI9 PI/160 PL-165 PL-21! - .. Adipate Elton PL-SOS PL-S04 * OtKor PUtflelien PL-400 PL-411-D PL-S1S PL-40 PL-117 PI/128 PL-S06 PL-511 CS-14 * (Chemical Specialties Data Report) General PL-107 PL-227 PL-151 UNT-ACH-SM.4/U TIH. SAKTiazea l-H Santicizer s Santicizer 8 Santicizer 9 SantolIte MHPand Sas'tolite MS-SO^fr ` Santicizer E-1S ** Santicizer B-16 ' Santicizer M-17 Tricresyl Phosphate Triphenyl Phosphate Santicizer 140 Santicizer 141 . Dibutyl Phthalate Dicydohexyl Phthalate Diethyl Phthalate and Dimethyl Phthalate Diitodecyl Phthalate " Diocty) Phthalatc Diphenyl Phthalate . Santicizer 160 .. . Santicizer 16$ Santicizer 21S . . . Diioodccyl Adipate Dioctyl Adipate . ' .... ' , . | . . - SANTtaZER 409 ' Santicizer 411 Mop-Epox ftt-40 Triphenyl Phosphite ' - Montar Compounds Aroclor Plasticizers Aroclor resins and plasticizers for chlorinate^ rubber ' Aroclor Fire-Retardant Plasticisers and Modifiers for Epoxy Resins . ;. ... * . ' | '! Monsanto Plasticisers in Synthctic-Resin Adhesives Monsanto Plasticisers in Protective Coatings Monsanto Modifier# for Thiol^ol Polysulfide Liquid Polymera 1 1 12 0221359 CD TOWOLDMON0005047 WATER_PCB-00001557 Gentlemen: - (date) . Please send me a copy of each indicated technical I bulletin containing additional detailed information bout Monsanto plasticizers for hard-to-plasticize resins: t PL- PL- PI^________________________________ | PL- PL- PL- Comments,__________ _: * ........... . Name! in.--.......... . . in.-- . in..M . . 5 Title__ .________________________ Company. __ _ J Adciraw ----- t City--_______________________ Zone. g * State! Gentlemen: 1 (date) Please send me a copy of each ndicated technics bulletin containing additional tt tailed informatio about Monsanto plasticizers fit hard-to-plasticii resins: ' PI- PI- PT. pi- pi. | PI- , rommenU Mi Title Address nty Stale ' o P 5 Gentlemen: (date) Gentlemen: date) r Please send me a copy of each indicated technical Please send me a copy of each idicated technics: bulletin containing additional detailed information bulletin containing additional d< ailed information about Monsanto plasticizers for hard.to-plastidze about Monsanto plasticizers foi hard-to-plasticizc O resins: resins: PL- PL- PL-._______________________________ _ PI- PT- PT- PL---:________ PL---!________ PL-- g Comments o Pi. Pi- PT1 _ z | Name: I Title^ Title ( Company o Address______________________________ j { CityZone. Pirv ; State o; ;tl3fc0 TOWOLDMON0005048 WATER_PCB-00001558 BUSINESS REPLY MAIL MONSANTO CHEMICAL COMPANY 'LASTICIZER COUNCIL, DEPT. PL-332 Organic Chemicals Division 300 North Lindbergh Boulevard St. Louis 66, Missouri FIRST CLASS Pferfaifr N*. 3316 ST. LOUIS. MO. BUSI NESS REPLY MAIL MONSANTO CHEMICAL COMPANY PLASTICIZER COUNCIL, DEPT. PL-332 Organic Chemicals Division 800 North Lindbergh Boulevard St. Louis 66, Missouri RftST CLASS FwmH No. 3016 ST. LOUIS, MO. BUSINESS REPLY MAIL i ; ;; MONSANTO CHEMICAL COMPANY PLASTICIZER COUNCIL, DEPT. PL-332 i :_ j Organic Chemicals Division , ijj 800 North Lindbergh Boulevard ' ! : St. Louis 66, Missouri 3 2 ------- -- ;_____ ------- - BUSINESS REPLY MAIL MONSANTO CHEMICAL COMPANY.. PLASTICIZER COUNCIL, DEPT. PL-332 Organic Chemicals Division : , 800 North Lindbergh Boulevard : St. Louis 66, Missouri FIRST CLASS fwmit No. 3016 ST. LOUIS. MO. PLEASE REQUEST SAMPLES ON YOUR COMPANY LETTERHEAD I TOWOLDMON0005049 WATER_PCB-00001559