Document 5bYyeGeQNJBMqKN01wk3v6kpe

I~..... Monsanto Chemicals ....k.4 .. AROCLORS As Used in Chlorinated Rubber Monsanto Technical Bulletin No. P-124 January 1, 1948 Monsanto Chemical Company, St. Louis 4, Mo. AROCLORS As Used in C hlorinated Rubber AROCLORS*, chlorinated biphenyl and chlorinated poly-phenyls, are effective plasti cizers and resins for chlorinated rubber base lacquers, varnishes and paints. These protective coatings are used where flame resistance, corrosion resistance, chemical resistance, i.e., resistance to acids, alkalies and water, and good electrical insulating properties are required. Some of the important applications for these protective and decorative coatings for wood, metal, brick, stone, concrete and fabric surfaces include: 1. Wood and metal used in the construction of yachts, barges and other marine craft. 2. Structure! steel for bridges, buildings, roofs and power-line structures. 3. Structural materials used at chemical plants, pulp and paper mills, textile mills, petroleum refineries and gas works where protection against acid fumes, alkalies and gas is essential. 4. For the protection of tank cars and other rolling stock and construction machinery against corrosive materials and weathering. 5. To protect equipment used in electroplating and as stop-off lacquers in this industry. 6. Masonry floors and walls. Concrete swimming pools and traffic paints. 7. As cable coatings requiring nonflammability, chemical resistance, water resistance and excellent electrical properties. 8. Coatings for cloth to impart "waterproofing" qualities as well as chemical and flame resistance. * Registered in U. S. Patent Office. > Zc > O / >z -4 o o 00 X wcr z o The Information In Ihli bulletin U boied on out expedience, represents our belt judgment In the matter, and It Intended to be helpful; but we cannot aitume reipomlbility for any loti or accident that may reiuft from It* vie. 0b0B36B TOWOLDMONOQ33933 AROCLORS AS USED IN CHLORINATED RUBBER I. INTRODUCTION 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 per cent. II. PROPERTIES OF CHLORINATED RUBBER The typical properties of Parlon as given by Hercules Powder Company, Wilmington, Delaware, are listed in the following Table I: General TABLE I. TYPICAL PROPERTIES OF PARLON Form as shipped ................ Color of film........................ Odor.................................... Clarity of film.................... Taste.................................... Moisture, per cent as shipped White granular powder Water white None Good None 0.5 maximum Physical Specific gravity............................................................................................ 1.64 Specific volume, as shipped, in cubic inches per pound........................ 16.9 Bulking value, gallons per pound............................................................... 0-0735 Index of refraction.................................................................................... 1.554 Electrical (clear unplasticizcd film*)' Specific surface resistance, ohms x io10....................................................2,000 Dielectric strength, volts per mil (A.S.T.M. method)............................ 2,300 Dielectric constant at 25C. and 1,000 cycles........................................ 3.1 Power factor at 25C. and 1,000 cycles.................................................... 0.0015 to 0.0030 Power factor at 25C. and 1,000 cycles, after immersion in water for 140 hours and surface wiped dry............................................................ 0.0027 Mechanical (clear unplasticized film*) 20-cp. type Tensile strength, pounds per square inch, dry............................ 4,270 Tensile strength, pounds per square inch, wet............................ 4,100 Elongation, per cent, dry................................................................ 3.6 Elongation, per cent, wet................................................................ 3.8 Modulus of elasticity, pounds per square inch............................ 1.4 x io6 Hardness, Sward index, per cent of glass.................................... 90 Flexibility of Parlon film increases with viscosity of Parlon used. 1,000-cp. type 4,850 4,360 3-3 3-4 Thermal (clear unplasticized film*) Burning rate.................................................................................... nonflammable Effect of dry heat on film............................................................ stable up to and at 125*0. Softening point................................................................................ decomposes at 135 to I50C. Physical-Chemical (clear unplasticized film*) Sunlight, effect of............................................................................ Discolors and embrittles Aging, effect of.................................................................................Very slight Water, hot, effect of.........................................................................Blushes Water, cold, effect of.................... ................................................None Moisture absorption (80% relative humidity for 24 hours), per cent.............................................................................................0.27 Moisture vapor permeability of 0.003-inch film (grams water/ square centimeter/0.01 centimeter/hour at 2i*C.) . . . . 0.2 x to4 * Films used in teBts were laid down from a toluene solution. 0808369 TOWOLDMONOQ33934 General resistance to: Acids, weak................................................................................... excellent Acids, strong....................................................................................... excellent Alkalies, weak....................................................................................excellent Alkalies, strong....................................................................................excellent Salt spray.........................................................................................good Alcohols............................................................................................... excellent Ketones............................................................................................ soluble Esters.................................................................................................soluble Hydrocarbons, aromatic................................................................... soluble Hydrocarbons, aliphatic.................................................................good Oils, mineral.....................................................................................good Oils, animal.................................................................................... poor Oils, vegetable................................................................................ poor Different viscosity types of Parlon and suggested uses are given in Table II. TABLE II. PARLON VISCOSITY TYPES Viscosity Type Viscosity Range (in centipoises) 5-cp. lo-cp. 20-Cp. I25-Cp. I,000-cp. 5 to 7 8 to 12 16 to 25 no to 190 800 to 2,000 Examples of actual or suggested applications of the several viscosity types are given: Type 5-cp. IO'Cp, 20-cp. 125-cp. 1,000-cp. Use Examples In printing inks and as a fortifier for alkyd resin enamels. In high-solids finishes and as a fortifier for alkyd resin and oleoresinous varnishes and enamels. As a film-former in protective coatings and as a fortifier in enamels and varnishes. As a film-former in protective coatings, in paper lacquers, adhesives, and textile 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 PARLON COMPOSITIONS 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 --3 0508370 TOWOLDMONOQ33935 MIXED SOLVENTS 70:30 97:3 83:17 41 :7 :35 : <7 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 : mineral spirits Ethyl acetate: isopentane Ethyl acetate : isopropyl acetate : Troluoil Methyl isobutyl ketone : Troluoil Hi-Flash solvent naphtha : turpentine Methyl acetate: isopentane Shell TS-28: xylene 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 containing 20 per cent of the plastics, using 2 :1 and 1 :1, Parlon : resin, ratios. Similarly, the plasticizer type Aroclor 1242, 1254 and 1260 show good miscibility in chlori nated 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 Parts by weight Parlon, 20-cp......................................... 16 16 12 Aroclor 5460........................................ .... 8 8 8 12 Dibutyl pnthalate................................ 4 Tung oil, Thermolyzed, 976 .... 5 Xylene or butyl acetate.................... .... .76 72 71 76 12 12 3 73 12 12 375 72.25 PLASTICIZER TYPE AROCLORS FOR PARLON PLASTICS Ingredients Parts by weight Parlon, 20-cp......................................... .... 20 20 20 Aroclor 1254 or 1260........................ .... 4 7 20 Xylene................................................ .... 76 73 70 Examination of the films cast from these lacquers revealed the following characteristics imparted by the Aroclors: Adhesion: -- 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 Transite surfaces. Other commercially available resins, particularly oil modified alkyd resins, tested in similar films gave better adhesion than Aroclor 5460 to such surfaces as glass, tin, copper, sealed wood and cellophane. The lacquer films plasticized with Aroclors 1254 or 1260 gave good adhesion to Transite, cello phane, galvanized iron and primed steel surfaces. Some of the other commercially available plasticizers tested in similar films gave better adhesion than the Aroclors 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 accomplished 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 per cent hydrochloric acid, 5 per cent sodium hydroxide, 5 per cent sodium chloride solutions and to water spot tests. --4-- 01>Od37l TOWOLDMONOQ33936 Film Hardness:-- Using Aroclor 5460 in ratios of 5 :10 and 10 : io, Aroclor : Parlon, decidedly softer films were produced than when other commercial resins were similarly 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. 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 1260 used as a plasticizer rates, in terms of cold-check resist ance, 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 containing Aroclors 5460, 1254 or 1260 have entirely satisfactory sanding and polishing characteristics. Wcatherability:--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 chlori nated 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 ultra violet light. However, there is considerable 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 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 as 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. TABLE IV. AROCLOR PLASTICIZER IN CHLORINATED RUBBER PAINTS FOR ALKALINE SURFACES (Examples of starting formulas) Materials Formula 1 for basement floors Formula 2 to meet Fed. Spec. TT-P-91 Formula 3 for swimming pools (Parts by weight) Parlon, 20-cp. type.................................... 18 18 14.6 Aroclor 1254................................................ Rezyl 869.................................................... Aroclor 5460 or Cumar Pio .................. 10 8 10 6 4.4 Beckosol3i................................................. Tung oil, Thermolyzed, 976.................... Titanium dioxide........................................ Zinc oxide.................................................... Silica flour..................................................... 16 2 3 2.9 4.4 16 19.7 2 6.5 Carbon black................................................ 0.2 0.5 Xylene............................................................ 42.8 47.5 Hi-Flash naphtha.................................................................................... 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. 47.5 0^08^72 TOWOLDMONOQ33937 TABLE V. AROCLOR PLASTICIZERS AND RESINS FOR CHLORINATED RUBBER, ACID AND ALKALI-RESISTANT FINISHES (Examples for starting formulations) Materials X For interior use against acids and alkalies Parlon, 20-cp. type................ Aroclor 5460............................ Bakelite XJ-12895.................... Rezyl 807 (solids).................... Aroclor 1254............................ Aroclor 1260............................ Tung oil, Thcrmolyzed, 976 . Iron oxide................................ Titanium dioxide.................... Zinc oxide................................ Zylene........................................ Hi-Flash naphtha.................... Toluene.................................... . . 6.4 8 53-6 2 For exterior For exterior ussir _ 4. For maximum resistance to acids and alkalies (Parts by weight) 16 16 18 6.4 6.4 4.8 4.8 8 6 4.8 4.8 16 16 18 52 52 39 11 For use against soap solutions 12 6 7-7 18 6 28 10.3 12 - Totals........................ IOO 100 100 100 The paints given in Table V were applied to metal bars or panels and tested. Formula i, an interior paint, showed good resistance to a io per cent hydrochloric acid solution and to a 5 per cent sodium hydroxide solution. The add resistant paint described under the heading of Formula 2 has shown excellent outdoor protection to metal surfaces on acid 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 resistance to acids, alkalies and other corrosive materials such as salt solutions. Moreover, this paint showed good adhesion to various surfaces including 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 I40F. C. Marin 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 usefulness of these paints to protect wood and metal used in making boats, barges and other marine equipment. A suggested formula for a marine paint is given in Table VI. TABLE VI. AROCLOR PLASTICIZER FOR A CHLORINATED RUBBER MARINE WHITE PAINT (Starting formulation) Materials Parts by weight Parlon, 20-cp. type................................................ Aroclor 1254............................................................ Rezyl 869................................................................ Titanium dioxide'.................................................... .. .. .. .. 20 6 6 25 Xylene.................................................................... Hi-Flash naphtha........................ ........................ .. .. 23 20 Total 100 --6-- 0808373 TOWOLDMONOQ33938 D. Emulsion Points: 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 per cent solution of Aerosol OT in distilled water or a 4 per cent solu tion 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 Parlon................ Aroclor 1254 . . Cumar Pio . . . Xylene .... Hi-Flash naphtha Total . Parts by weight 28 14 10 24 ... H., 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................ Total . . . 20 .6 .6 . 68 . 100 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 01 coating in these fields may be restricted especially where freedom from odor and taste are required. Unpigmented Aroclor and chlorinated rubber finishes would seem suitable for certain fabrics used indoors, but not ^here they are exposed to high temperatures and direct sunlight. O. Coatings for Electrical Apparatus: Because of their desirable electrical properties, compositions 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 alkali-resistant 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 examination of films laid down from 2 :1 and 1:1, Parlon : resin or plasticizer ratios at 20 per cent concentration in toluene. ObOB37<i TOWOLDMONOQ33939 TABLE VII. RESINS AND PLASTICIZERS MISCIBLE IN PARLON RESINS Ambcrol 801, 806P, ST-137, F7 Aroclor 1262, 5460 Aroplaz 920,930,935,940 Bakelite XR-3180, XR-4503, XR-4006, BR-2963, XJ-9868, BR-1329, BR-3360 Bcckacite 1112 Bcckaminc P-J38, P-254 Supcr-Beckamine 3501 Beckopol 1400 Bcckosol 1 (solid), 18, 31, 34,40,1329 Beetle Resin 227-8 Clorafin 70 Copal Cumar Pio Dammar Duraplex C-45-LV, C-48, C-49, C-50-LV, C-51, C-62, D-61, D-62, E-7i, E-71-A, E-73 East India gum Ester gum Ethyl Methacrylate Esterol 750 Forravar Gelva 2.5 Glyptal 1247,2450,2454,2458,2464,2466,2500 Lewiso! 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 Amylchloro naphthalene Amyl oleate Amyl stearate Aroclor 1242 Aroclor 1254 Aroclor 1260 Butyl myristate Butyl stearate Camphor Castor oil, raw Castor oil, dehydrated Castor oil fatty acid esters Cellosolve phthalate Coconut fatty acid esters Diamyl naphthalene Diamyl phthalate Dibutyl phthalate Dibutyl sebacate Diethyl phthalate Dimethyl phthalate Fish oil Hercolyn Linseed oil PLASTICIZERS Methyl cellosolve oleate Monoamyl naphthalene Naftolen Neville heavy oil No. 2 Nevillite oil Oiticica oil Palm fatty acid esters Peri11a oil Polyamyl naphthalene Resinous Products C-24 Santicizer B-16 Santicizer M-17 Sextol phthalate Sextol stearate Soya bean fatty acid esters Soya bean oil Thermoil A Tributyl phosphate Tricresyl 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 arc 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 applications for chlorinated rubber, then more detailed information about them will be given. -- 8-- Ob0837b TOWOLDMONOQ33940 VII. GENERAL Prior to Word 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 plas ticized chlorinated rubber compositions. Their principal field of application is as lacquers, varnishes and paints where flame resistance, cor rosion resistance, chemical resistance, i.e., resistance to acids, alkalies and water, and good electrical insulating properties are required. When properly pigmented these paints or coatings have good weatherability. 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 chlori nated 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 was 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 recom mendations or suggestions are made without guarantee, since the conditions of use are beyond our control. 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. MONSANTO CHEMICAL COMPANY Saint Louis 4, Missouri New York Chicago Boston Birmingham Charlotte Cincinnati Philadelphia Detroit Los Angeles * San Francisco Montreal rh/rOS-JM--71 --9-- Printed in U.$>. 0b063?6 TOWOLDMONOQ33941