Document ga0d2xYqQ1LROdDoZ4Dyn136Q

.0 ' // MONSANTO TECHNICAL BULLETIN No~ -124_____ -- October 28, 1947 Monsanto Chemical Company Saint Louis, Missouri New York-Chicago-Boston-Birmlngham-Charlotte-Cincinnati-PhlladelphlaDetrolt-Los Angeles-San Franclsco-Montreal I. INTRODUCTION The Aroclors*, chlorinated biphenyl and chlorinated poly-phenyls, are used effectively as resins and plasticizers to Impart desired qualities to chlorinated rubber, such as Hercules' Parlon. Parlon is made by chlorinating natural rubber, yielding a mixture of two polymers possessing an average chlorine content of 67 percent. II. PROPERTIES OP CHLORINATED RUBBER The typical properties of Parlon as given by Hercules Powder Com pany, Wilmington, Delaware are listed in the following Table I: TABLE I. TYPICAL PROPERTIES OP PARLON General Form as shipped Color of film Odor Clarity of film Taste Moisture, percent as shipped White granular powder Water white None Good None 0.5 maximum Physical Specific gravity Specific volume, as shipped, in cubic inches per pound Bulking value, gallons per pound Index of refraction 1.64 16.9 O.O735 1.554 * Registered in U. S. Patent Office. OZZlllb TOWOLDMON0026756 WATER_PCB-00011225 -2- Electricel (clear unplasticized film*) Specific surface resistance, ohms x 10"10 - Dielectric strength, volts per mil (A.S.T.M. method) Dielectric constant at 25C. and 1,000 cycles Pover factor at 25C. and 1,000 cycles Pover factor at 25C. and 1,000 cycles, after Immersion In vater for 140 hours and surface wiped dry 2,000 2,300 3-1 0.0015 to 0.0030 0.0027 Mechanical (clear unplastlcized film*) 20-cp. type 1,000-cp. type Tensile strength, pounds per square inch, dry Tensile strength, pounds per square inch, vet Elongation, percent, dry Elongation, percent, vet Modulus of elasticity, pounds per square inch Hardness, Sward index, percent of glass 4,270 4,100 3.6 3-6 1.4 x lo5 90 4,850 4,360 3-3 3-4 Flexibility of Parlon film increases with viscosity of Parlon used. Thermal (clear unplastlcized film*) Burning rate Effect of dry heat on film Softening point nonflammable stable up to and at 125C. decomposes at 135 to 150C. Physical-Chemical (clear unplastlcized film*) Sunlight, effect of Aging, effect of Vater, hot, effect of Water, cold, effect of . Moisture absorption (80$ relative humidity for 24 hours), percent Discolors and embrittles Very slight Blushes None 0.27 0222137 Films used in tests were laid down from a toluene solution. TOWOLDMONOQ26757 WATER_PCB-00011226 o -3- Moisture vapor permeability of 0.003-Inch film (grams vater/ square centimeter/0.01 centimeter/ hour at 21C.) , serai resistance to: Acids, veak Acids, strong Alkalies, weak Alkalies, strong Salt spray Alcohols Ketones Esters Hydrocarbons, aromatic Hydrocarbons, aliphatic Oils, mineral Oils, animal Oils, vegetable . 0.2 x 10- excellent excellent excellent excellent good excellent soluble soluble soluble good good poor poor Different viscosity types of Parlon and suggested uses are given in Table II. TABLE II. Viscosity Type PAPLON VISCOSITY TYPES Viscosity Range (in centlpoi3es) 5-cp. 10-cp. 20-cp. 125-cp. 1,000-cp. 5 to 7 8 to 12 16 to 25 110 to 190 800 to 2,000 Examples of actual or suggested applications of the several viscosity types are given: Type Use Examples 5-cp. In printing inks and as a fortifier for alkyd resin enamels. 10-cp. In high-solids finishes and o as a fortifier for alkyd resin and oleoresinous varnishes and enamels. TOWOLDMON0026758 WATEFLPCB-00011227 o -4- 20-op. 125-cp. 1,000-cp. As a film-former in protective coatings and a3 a fortifier in enamels and var nishes. ' As a'film-former in protective coatings, in paper lacquers, adhesives, and tex tile finishes. As a film-former in adhesives, textile finishes, and other finishes where flexibility is important. III. SUGGESTED SOLVENTS FOR AROCLOR AND CHLORINATED RUBBER COMPOSITIONS Solvents and solvent mixtures suggested for use in preparing Aroclor and Parlon formulations are given in the following Table III: TABLE IIIjmrSmUGwGoESirTzEDfflSFOoLVsErNnTmS sFOR AROCLOR Solvents Amsco Solv, B and E Amyl acetate Butyl acetate Carbon tetrachloride Cellosolve Diacetone alcohol Diethyl carbonate Ethyl acetate Ethylene dichloride Hi-Flash naphtha Methyl acetate Methyl ethyl ketone Methyl isobutyl ketone Methyl salicylate Notol Octyl acetate Sovasol Nos. 74, 75 Solvesso 100 Tollac Toluene Union Aromatic Solvent 3553-10 Union Solvent No. 30 Xylene Mixed Solvents 70:30 97:3 83:17 41:7:35:17 .30:70 18:59:23 64:36 30:30:40 40:60 30:70 70:30 85:15 acetone:hexane acetone:mineral spirits ` benzene:isopentane - Cellosolve:ethanol (anhydrous): ethyl acetaterxylene Cellosolve:turpentine Cellosolve: turpentine .-mineral spirits ethyl acetate:Isopentane ethyl acetate.-Isopropyl acetate:Troluoll methyl i3obutyl ketone:Troluoll Hi-Flash solvent naphtha:turpentine Methyl acetate:isopentane Shell TS-2S:xylene 02Z2139 TOWOLDMON0026759 WATER_PCB-00011228 -5- IV. AROCLOR AND CHLORINATED RUBBER, PLASTICS FILMS The resinous Aroclors 1262 and 5460 show good miscibility with chlorinated rubber films as laid down from toluene solution con taining 20 percent of the plastics, using 2:1 and 1:1, Parlon: resin, ratios. Similarly, the plasticiser type Aroclor 1242, 1254 and 1260 show good miscibility in chlorinated rubber. The properties of film3 derived from the following formulations containing either Parlon and resinous Aroclors 1262 or 5460, or Parlon and the plasticizer type Aroclors 1242, 1254 or 1260 were studied. RESINOUS TYPE AROCLOR FOR PARLON PLASTICS Ingredients ________ ________ Parts by weight Parlon, 20-cp. Aroclor 5460 Dlbutyl phthalate Tung oil, Thermolyzed, 976 Xylene or butyl acetate 16 8 76 16 8 4 72 16 12 12 8 12 12 3 5 71 76 73 12 12 3.75 72.25 PLASTICIZER TYPE AROCLORS FOR PARLON PLASTICS Ingredients Parlon, 20-cp. Aroclor 1254 or 1260 Xylene Parts by weight 20 20 47 76 73 20 20 70 ^140 I TOWOLDMON0026760 WATER_PCB-00011229 o 6- - Fxamination of the films cast from these lacquers revealed the fol loving characteristics imparted by the Aroclors: Adhesion; - Unplasticized chlorinated rubber films have very poor adhesive qualities. The lacquer film containing Aroclor $k6o gave good adhesion to aluminum, bare steel, primed steel, galvanized iron and Transite surfaces. Other commercially available resins, parti cularly oil modified alkyd resins, tested in similar films gave better adhesion than Aroclor 5460 to such surfaces as glass, tin, copper, sealed vood and cello phane . The lacquer films plasticized with Aroclors 1254 or 1260 gave good adhesion to Transite, cellophane, gal vanized iron and primed steel surfaces. Some of the other commercially available plasticizers tested in similar films gave better adhesion than the Arodlors to aluminum, tin, bare steel, copper and sealed vood surfaces. 0 Aroclors, alone, possess pronounced adhesive qualities. Doubtless, vhere the objective is to produce adhesives, by varying the Aroclor content or by using a mixture Of Aroclors in the chlorinated rubber lacquers, much better adhesion to all of the surfaces would be accom plished than was the case with the type of plastics films studied. Resistance to Aqueous Solutions; Aroclors 1254 or 1260 used as plasticizers and Aroclor 5460 used as a resin in chlorinated rubber produced plastics films possessing satisfactory resistance to 10 percent hydrochloric acid, 5 percent sodium hydroxide, 5 percent sodium chloride solutions and to water spot tests. Film Hardness; - Using Aroclor 5460 in ratios of 5:10' and 10:10, Aroclor; Parlon, decidedly softer films were produced than when other commercial resins were simi larly used. Likewise, Aroclors 1254 or 1260 used in ratios of 2:10 and 5:10, Aroclor: Parlon, gave softer films than obtained from other commercial plasticizers, used at these concentrations. This indicates the strong plasticizing action of these Aroclors on chlorinated rubber. TOWOLDMON0026761 WATER_PCB-00011230 -7- Cold-Check Resistance: - Regarding cold-check resistant qualities Imparted to chlorinated rubber films, Aroclor 5^60 Is somewhat superior to Bakellte type resins, but not as good as long-oil modified alkyds, Aroclor 1260 used as a plasticizer rates. In terms of cold-check re sistance, somewhat better than Aroclor 1251* and nearly as good as the best of the other plasticizers studied for this property. Miscellaneous Properties; - Parlon plastics films con't'eln'ing Aroclors 5460, 1251* or 1260 have entirely sat isfactory sanding and polishing characteristics. Weatherability: - Pigmented chlorinated rubber finishes containing Aroclors have consistently shown good outdoor weatherability. However, similar unpigmented finishes, regardless of the plasticizer or resin used and also in the absence of these additives, have been found to give poor outdoor weathering. Relatively poor resistance to ultraviolet light is a weakness of chlorinated rubber. Most pigments, with the exception of ultra-marine blue are usable with Parlon finishes and are recommended when the coating is to be subjected to outdoor weathering or exposed to ultraviolet light. However, there is consi derable variation regarding the protection offered by different pigments. Inspection of Parlon-fortified alkyd enamels showed the weatherability varied from 63 months for the enamel pigmented with chrome green to % months for enamel pigmented with a titanium dioxide-iron blue combination. V. USES FOR AROCLORS IN CHLORINATED RUBBER COATINGS A. Finishes for Alkaline Surfaces: ' Aroclors, as well os chlorinated rubber, are highly resistant against alkalies and moisture. Because of these properties paints based on Aroclor and chlorinated rubber combinations are used in large quantity for application to concrete floors, walls, swimming pools, etc. Examples of this type of paint are given in Table IV. TOWOLDMON0026762 WATER_PCB-00011231 o 8- - TABLE IV. AROCLOR PLASTICIZER IN CHLORINATED RUBBER -------------------- FCTT5~PoiV' aLKaLIW SURFACES' (Examples of starting formulas) Parts by weight Formula 1 Formula 2 to Formula 3 for base- meet Fed. Specif, for svlm- Materials_______________ ment floors TT-P-91______________ mlng pools Parlon, 20-cp. type Aroclor 1254 Rezyl 869 Aroclor 5460 or Cumar P10 Beckosol 31 Tung oil, Thermolyzed, 976 18 10 8 18 10 6 14.6 4.4 2-9 4.4 Titanium dioxide Zinc oxide Silica flour Carbon black 16 2 3 0.2 16 2 0.5 19.7 6.5 Xylene Hi-Flash naphtha 42.8 47.5 47.5 Totals 100 100 100 B. Acids and Alkali-Resistant Finishes: Particular care must be exercised In the choice of resins and plasticizers for use In chemical resistant paints. For this purpose, Aroclors are outstanding and are being used successfully in the acid and alkali-resistant chlorinated rubber formulations given in Table V. o TOWOLDMON0026763 WATER_PCB-00011232 -9- TABLE V. AROCLOR PLASTICIZERS AND RESINS FOR CHLORINATED RUBBER, ------------ABUT aUIT ALK;,LI-RESISTA'Nr"F7HTSHES----------- (Examples for starting formulations) Materials 12 3 For lnte- For exte- For exte- rlor use rior use rior use against against against acids and acids alkalies alkalies 4 For maximum resistance to acids and alkalies 5 For use against soap solutlons (Parts by weight) Parlon, 20-cp. type 16 Aroclor 5460 6.4 Bakelite XJ-I3895 Rezyl 807 (solids) 16 6.4 16 6.4 18 12 6 Aroclor 1254 Aroclor 1260 Tung oil, Ther- molyzed, 976 Iron Titanium dioxide Zinc oxide 8 16 4.8 4.8 16 4.8 4.8 16 8 6 18 7.7 18 6 Xylene Hi-Flash naphtha Toluene 53.6 52 52 39 11 28 10.3 12 Totals 100 100 100 100 100 The paints given in Table V were applied to metal bars or panels and tested. Formula 1, an Interior paint, shoved good resistance to a 10 percent hydrochloric acid solution and to a 5 percent sodium hydroxide solution. The acid resistant paint described voider the heading of Formula 2 has shown excellent outdoor protection to metal surfaces on 02221** TOWOLDMON0026764 WATER_PCB-00011233 10- o acld manufacturing plants. Similarly, paints based on Formula 3 have given good outdoor performance on alkali producing plants. Paint based on Formula 4 was found to have excellent resistant to acids, alkalies and other corrosive materials such as salt solutions. Moreover, this paint showed good adhesion to various surfaces In cluding glass. Paint based on Formula 5 is indicated to have good resistance against warm aqueous solutions containing soap. It should be pointed out that Aroclor and chlorinated rubber finishes are not recommended for continuous exposure at temperatures above 140F. C. Marine Finishes: Aroclor plasticized chlorinated rubber coatings possess good resistance to salt water and their hard finish deters algae and marine growths from adhering to them. These qualities and good chemical resistance indicates the use fulness of these paints to protect wood and metal used in making boat3, barges and other marine equipment. A sug gested formula for a marine paint is given In Table VI. TABLE VI, AROCLOR PLASTICIZER FOR A CHLORINATED RUBBER MARTHITBHrTirTAlIT (Starting formulation) Materials Parlon, 20-cp. type Aroclor 1254 Rezyl 869 Titanium dioxide Xylene Hi-Flash Naphtha Total Parts by weight 20 6 6 25 23 20 100 0222i*5 TOWOLDMON0026765 WATER_PCB-00011234 -11- D. Emulsion Paints: Aroclor 1254 Is used In chlorinated rubber emulsion paints recommended vhen chemical resistance is required on porous surfaces. Hercules Powder Company report that the preferred water phases for such paints are either a 1 percent solution of Aerosol OT in distilled water or a 4 percent solution of sodium oleate in distilled water. For the complete emulsion, a ratio by weight of lacquer phase to water phase of 2.5 to 1 is suggested. Parlon of any desired viscosity may be used. A typical paint phase for the Aroclor-Parlon emulsion paint contains the following ingredients: Paint Phase for the Emulsion Ingredients______ Parts by weight Parlon Aroclor 1254 Cumar P10 Xylene Hi-Flash naphtha 28 14 10 24 24 Total 100 E. Adhesives; Aroclor and chlorinated rubber adhesives are resistant to chemicals and were developed originally for adhering labels to acid bottles. These adhesives are also of unusual interest because of their good fire resistant qualities. A typical formulation contains the following ingredients: Aroclor Plasticizers for Chlorinated Rubber Adhesives Ingredients____________________ Parts by weight Parlon, 125-cp. type Aroclor 1254 Aroclor 1260 Toluene 20 6 6 68 Total 100 02Z2I',b TOWOLDMON0026766 WATER_PCB-00011235 o -12- F. Paper and Textile Coatings: Aroclor and chlorinated rubber coatings are worthy of consideration for specific end uses In the paper and textile coatings fields. In general, however, the use of this type of coating In these fields may be restricted especially where freedom from odor and taste are required. Unplgmented Aroclor and chlorinated rubber finishes would Beem suitable for certain fabrics used indoors, tut not where they are exposed to high temperatures and direct sunlight. G. Coatings for Electrical Apparatus: Because of their desirable electrical properties, composi tions containing Aroclors and chlorinated rubber are very useful to Insulate and protect electrical wire and apparatus from moisture. When fortified with selected fungistats and waxes, coatings of this type are used to "tropicalize" or protect electronic equipment against both moisture and fungi. Moreover, the fire resistant qualities of these plastics are highly desirable for use in the electrical field. H. Inks: Aroclor plasticized chlorinated rubber compositions are very useful for printing inks where faster drying time and increased chemical resistance are desired. The alkaliresistant properties of such plastics suggest their use in the printing of soap wrappers and soap boxes, bottle labels and other commodities uhere the ink must be resistant to alkalies. VI. RESINS AND PLASTICIZERS, OTHER THAN AROCLOR, MISCIBLE IN CHLORINATED RUBBER " The resins and plasticizers given in the following Table VII are miscible in chlorinated rubber. This was determined by the ex amination of films laid down from 2:1 and 1:1, Parlon: resin or plasticizer ratios at 20 percent concentration in toluene. o 02221*7 TOWOLDMON0026767 WATER_PCB-00011236 TABLE VII. RESINS AMD PLASTICIZERS MISCIBLE IN PARLON .. Resins Amberol 801,8o6P,ST-137,F7 Aroclor 1262,5460 Aroplaz 920,930,935,940 ,, ' Bakelite XR-3l8o,XR-4503,XR-4oo6,BR-2963,XJ-9868, BR-1329,BR-336o Beckacite 1112 Beckamine P-138, P-254 Super-Beckamlne 3501 Beokopol 1400 Beckosol 1 (solid),18,31,34,40,1329 Beetle Resin 227-8 Clorafin 70 Copal Cumar P10 Dammar Duraplex C-45-LV.C-48,C-49,C-50-LV,C-51,C-62,D-6l, D-62,E-71,E-71-A,E-73 East India gum EBter gum Ethyl Methacrylate Esterol 750 Formvar Gelve 2.5 Glyptal 1247,2450,2454,2458,2464,2466,2500 Lewisol 2L,28,33 Methyl Methacrylate Polymers Neville R-3,R-10 Pentalyn A,G,M,X Petrex 1, 130H Phenac 633-M Rezyl 116,X315,412,775,803,807,829,869,880,1103 Rosin Santolite MHP Staybelite Ester 1,2,10 Staybelite resin Super-Beckacite 1001 Syntex HI,H3,H12,17,213,22,28,29,32,36 Teglac 15,Z-152 Velsicol AD6-3 Vinsol 0 TOWOLDMON0026768 WATER_PCB-00011237 -14- Plaatlclzers Amylchloro naphthalene Amyl oleate Amyl stearate ' Aroclor 1242 Aroclor 1254 Aroclor 1260 Butyl myristate Butyl stearate Camphor Castor oil, rav Castor oil, dehydrated Castor oil fatty acid esters Cellosolve phthalate Coconut fatty acid esters Diamyl naphthalene . Diamyl phthalate Dlbutyl phthalate Dibutyl sebacate Diethyl phthalate Dimethyl phthalate Fish oil Hercolyn Linseed oil Methyl Cellosolve oleate Monoamyl naphthalene Naftolen Neville Heavy Oil No. 2 Nevillite oil Oticica oil Palm fatty acid esters Perllla oil Polyamyl naphthalene Resinous Products C-24 Santicizer B-16 Santiclzer M-17 Sextol phthalate Sextol stearate Soya bean fatty acid esters Soya bean oil Thermoil A Tributyl phosphate Trlcresyl phosphate Triethyl citrate Triphenyl phosphate Tung oil, Thermolyzed,976 The strong points and limitations of the resins and plasticizers given in Table VII relative to the properties they impart to chlorinated rubber are known. None give the important over-all desired qualities attained by the use of Aroclors. If occasion arises to consider the use of these materials in specific appli cations for chlorinated rubber, then more detailed Information about them will be given. VII. GENERAL Prior to World War II Aroclors, used in substantial amount with chlorinated rubber, made rapid growth in the applications given In this report. During the war, scarcity of natural rubber curtailed these developments but since the war industry has been quick to resume the use of Aroclor plasticized chlorinated rubber composi tions. Their principal field of application Is as lacquers, varnishes and paints where flame resistance, corrosion resistance, chemical resistance, i. e., resistance to acids, alkalies and vater, and good electrical insulating properties are required. TOWOLDMON0026769 WATER_PCB-00011238 o -15- Vhen properly pigmented these paints or coatings have good weatherabllity. Although the adhesion of unplasticized chlorinated rubber films to common structural materials is poor, when plasticized with Aroclors strong adhesive bonds are obtained. Aroclors Improve the flexibility and life of chlorinated rubber plastics coatings. The formulations of Aroclors and chlorinated rubber along with their suggested uses, as given in this report, are in line with good commercial practice. Much of the data given vas obtained from other firms, particularly Hercules Powder Company, Wilmington, Delaware. The information given is to serve as a guide or starting point in the development of formulations to expand taking advantage of the outstanding qualities of Aroclors as resins and plasticizers for chlorinated rubber. ***#*** The information contained in this bulletin is to our best knowledge true and accurate, but all recommendations or suggestions are made without guarantee, since the conditions of use are beyond our con trol. Monsanto Chemical Company disclaims any liability incurred in connection vith the use of these data or suggestions. Furthermore, nothing contained herein shall be construed as a recommendation to use any product in conflict with existing patents covering any material or its use. o rh/PCB 0222^ TOWOLDMON0026770 WATER_PCB-00011239