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-it u /. MONSANTO TECHNICAL BULLETIN No-<T-12.4 October 28, 1947 Monsanto Chemical Company Saint Louis, Missouri New York-Chicago-Boston-Birmingham-Cheriotte-Cincinnati-PhiladelphlaDetrolt-Los Angeles-San Franclsco-Montreal AR0CLORS._AS_USEI)..IN. CHLORINATED RUBBER 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 OF 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 OF PARLOR 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 inchesper pound Bulking value, gallons per Pound Index of refraction 1.64 16.9 0.0735 1.554 * Registered in U. S. Patent Office. 061371 TOWOLDMON0037917 WATER_PCB-00022386 -2- Electrical (clear unpla.sticized film*) Specific surface resistance, ohms x 10"10 Dielectric strength, volts per mil (A.S.T.M. method) Dielectric constant at 25C. snd 1,000 cycles Pover factor at 25C. and 1,000 cycles Pover factor at 25C. and 1,000 cycles, after immersion in water for 140 hours and surface wiped dry 2,000 2,300 3.1 0.0015 to 0.0030 0.0027 Mechanical (clear unplasticized film*) 20-cp. type 1,000-cp Tensile strength, pounds per square inch, dry Tensile strength, pounds per square inch, wet Elongation, percent, dry Elongation, percent, wet Modulus of elasticity, pounds per square inch Hardness, Sward index, percent of glass 4,270 4,100 ' 3.6 3.8 1.4 x :105 90 4,850 4,360 3.3 3.4 Flexibility of Parlon film Increases with viscosity of Parlon used. Thermal (clear unplasticized 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 unplasticized film*) Sunlight, effect of Aging, effect of Water, 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 % v *Fllms used in tests vere laid down from a toluene solution. 0613719 | TOWOLDMON0037918 WATER_PCB-00022387 -3- Moisture vapor permeability of 0.003-inch film (grams water/ square centimeter/0.01 centimeter/ hour at 21C.) neral resistance to: Acids, weak 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 IIo PARLON VISCOSITY TYPES Viscosity Type Viscosity Range (in centipolses) 5-op. 10-cp. 20-cp, 125-op. 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-op. In printing inks and as a fortifier for alkyd resin enamels. 10-cp. In high-solids finishes and 'Tk. as a fortifier for alkyd resin and oleoreslnous varnishes and enamels. 0613720 | TOWOLDMON0037919 WATER_PCB-00022388 -4- 20-cp. 125-OP. 1,000-op. As a film-former In protective coatings and as 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 III. SUGGESTED SOLVENTS FOR AROCLOR ---------------- AND PARL0Tl~S(5MP0SITIoUS------------ - Solvents Amsco Solv, B and E Amyl acetate Butyl acetate Carbon tetrachloride Cellosolve Dlacetone 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 acetate:xylene Cellosolve:turpentine Cellosolve:turpentine smineral spirits ethyl acetate:Isopentane ethyl acetate:isopropyl acetate:Troluoll methyl lsobutyl ketone:Troluoll Hi-Flash solvent naphtha:turpentine Methyl acetate:isopentane Shell TS-28:xylene 0613721 | TOWOLDMON0037920 WATER_PCB-00022389 -5- IV. AROCLOR AND CHLORINATED RUBBER, PLASTICS FILMS The resinous Aroclors 1262 and 5^*60 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 films 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 Parlon, 20-cp. Aroclor 5460 DIbutyl phthalate Tung oil, Thermolyzed, 976 Xylene or butyl acetate 16 8 76 16 8 4 72 Parts by weight 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 0613722 | TOWOLDMON0037921 WATER_PCB-00022390 -6- Fxamlnation of the films cast from these lacquers revealed the fol lowing characteristics imparted by the Aroclors: Adhesions - Unplasticized chlorinated rubber films have very poor adhesive qualities. The lacquer film containing Aroclor 5460 gave good adhesion to aluminum, bare steel, primed steel, galvanized iron and Translte 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 wood and cello phane . The lacquer films plasticized with Aroclors 1254 or 1260 gave good adhesion to Translte, cellophane, gal vanized iron and primed steel surfaces. Some of the other commercially available plasticizers tested in similar films gave better adhesion than the Arofelors to aluminum, tin, bare steel, copper and sealed wood surfaces. Aroclors, alone, possess pronounced adhesive qualities. Doubtless, where 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 s ~ 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. ObtT723 | TOWOLDMON0037922 WATER_PCB-00022391 -7- Cold-Check ResIstance: - Regarding cold-check resistant qualities imparted to chlorinated rubber films, Aroclor 5460 is somewhat superior to Bakelite type resins, but not as good as long-oil modified alkyds. Aroclor I960 used as a plasticizer rates, in terms of cold-check re sistance, somewhat better than Aroclor 1254 and nearly as good as the best of the other plasticizers studied for this property. Miscellaneous Properties: - Parlon plastics films con taining Aroclors 546t>, 1254 or 1260 have entirely sat isfactory sending and polishing characteristics. Weatherablllty: - Pigmented chlorinated rubber finishes 'containing Aroclors have consistently shown good outdoor weatherablllty. 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 Farlon-fortlfied slkyd enamels showed the weatherablllty varied from 63 months for the enamel pigmented with chrome green to 4 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 ore used in large quantity for application to concrete floors, walls, swimming pools, etc. Examples of this type of paint are given In Tsble IV. | TOWOLDMON0037923 WATER_PCB-00022392 -8- TABLE IV. AROCLOR PLASTICIZER IN CHLORINATED RUBBER ------------------- PAINTS FOR mim SURFACES-------------------- (Examples of starting formulas) Parts by weight Formula 1 Formula 2 to Formula 3 for base- meet Fed. Specif, for swim- Materlals________________ 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 Xylene Hi-Flash naphtha Totals 16 2 3 0.2 42.8 100 16 2 0.5 47.5 100 19-7 6.5 47.5 100 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. v 0613725 | TOWOLDMON0037924 WATER_PCB-00022393 -9- TABLE V. AROCLOR PLASTICIZERS AND RESINS FOR CHLORINATED RUBBER, ----------------------- J85TO AWrami-RESTSTANT FINISHES-------------------------- (Examples for starting formulations) Materials 1 23 For lnte- For exte - For exterior use rior use rior use against agalns t against acids and acids alkalies alkalies 4 For maximum resls- tance to acids and alkalies 5 For use against soap sol tions (Parts by weight) Parlon, 20-cp. type 16 16 16 18 12 Aroclor 5460 6.4 Bakelite XJ-I3895 Rezyl 807 (solids) 6.4 6.4 6 Aroclor 1254 Aroclor 1260 Tung oil, Ther- molyzed, 976 Iron Titanium dioxide Zinc oxide Xylene Hi-Flash naphtha Toluene 8 16 53.6 4.8 4.8 16 52 4.8 4.8 16 52 8 6 18 39 11 7.7 18 6 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, showed good resistance to a 10 percent hydrochloric acid solution and to a 5 percent sodium hydroxide solution. The acid resistant paint described under the heading of Formula 2 has shown excellent outdoor protection to metal surfaces on 061372b | TOWOLDMON0037925 WATER_PCB-00022394 -10- 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 surfaoes 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 boats, 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 ~MARIN6~TfflIlrE~TAlfrir (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 OfcU727 | TOWOLDMON0037926 WATER_PCB-00022395 -11- D. Emulsion Paints: Aroclor 1254 Is used in chlorinated rubber emulsion paints recommended -when 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-Farlon 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 TOWOLDMON0037927 WATER_PCB-00022396 -12- E. Paper and Textile Coatings: Aroolor and chlorinated rubber coatings are worthy of consideration for specific end uses in the paper end textile coatings fields. In general, however, the use of this type of ooating in these fields may be restricted especially vhere freedom from odor and taste are required. Unpigmented Aroolor and chlorinated rubber finishes would seem suitable for certain fabrics used indoors, but not vhere they are exposed to high temperatures and direct sunlight. G. Ooatlngs 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 molBture. 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 where 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. cv** | TOWOLDMON0037928 WATER_PCB-00022397 -13- TABLK VII, RESINS AMD PLASTICIZERS MISCIBLE IN PARLON Resins Amberol 801,806P,ST-137,F7 Aroclor 1262,5460 Aroplaz 920,930,935,940 Bakellte XR-3l80,XR-4503,XR-4006,BR-2963,XJ-9868, BR-1329,BR-336o Beokacite 1112 Beokamine P-138, P-254 Super-Beckamine 3501 . Beckopol 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-7l,E-71-A,E-73 East India gum Ester gum Ethyl Methacrylate Esterol 750 Formvar Gelva 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 Staybellte Ester 1,2,10 Stsybelite resin Euper-Beckacite 1001 Syntex HI,H3,H12,17,213, 22,28,29,32,36 Teglac 15,Z-152 Velsicol AD6-3 Vlnsol 0613730 | TOWOLDMON0037929 WATER_PCB-00022398 -14- Plasticizers Amylchloro naphthalene Amyl oleate Amyl stearate Aroolor 1242 Aroclor 1254 Aroclor 1260 Butyl myristate Butyl stearate Camphor CaBtor oil, raw Castor oil, dehydrated Castor oil fatty acid esters Cellosolve phthalate Coconut fatty acid esters Diamyl naphthalene Diamyl phthalate Dibutyl phthalate Dlbutyl sebacate Diethyl phthalate Dimethyl phthalate Pish oil Hercolyn Linseed oil Methyl Cellosolve oleate Monoamyl naphthalene Kaftolen Neville Heavy Oil No. 2 Nevlllite oil Cticica oil Palm fatty acid esters Perllla oil Polyamyl naphthalene Resinous Products C-24 Santiclzer B-16 Santiclzer M-17 Sextol phthalate Sextol stearate Soya bean fatty acid esters Soya bean oil Thermo!1 A Tributyl phosphate Tricresyl phosphate Trlethyl 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 water, and good electrical insulating properties are required. 0fell131 TOWOLDMON0037930 WATER_PCB-00022399 -15- When properly pigmented these paints or coatings have good weatherability. Although the adhesion of ur.plasticized chlorinated rubber films to common structural materials is poor, when plasticized vith Aroclors strong adhesive bonds are obtained. Aroclors improve the flexibility and life of chlorinated rubber plastics coatings. The formulations of Aroclors end chlorinated rubber along vith their suggested uses, as given in this report, are in line vith 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. ***-X-H** 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 with 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. rh/PGB 0bl37iZ I TOWOLDMON0037931 WATER_PCB-00022400