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QuiS/o r\ AROCLOR Co ?> Refills and Plasticizers for Chlorinated Rubber Technical Bulletin 0-124 May, 1957 Monsanto Chemical Company, Organic Chemicals Division, $!. Louis 1, Mo. Introduction Monsanto produces a series of chlorinated biphenyls and polyphenyls identified by the trademark Aroclor* for use as plasticizers and resins for chlorinated rubber base lacquers, varnishes and paints. These protective coatings are fire resistant, corrosion resistant, chemical resistant (to acids, alkalies and water), and have good electrical insulating properties. When properly pigmented, these coatings have good weatherability. Chlorinated rubber films plasticized with an Aroclor grip common structural materials in strong adhesive bonds. Addition of an Aroclor improves the flexibility and life of chlorinated rubber and plastic coatings. The formulations suggested in this bulletin are common in commercial practice. They are given as a starting point or guide in developing formulations that expand the outstanding qualities of these compounds. Aroclor; Monsanto Trademark. Reg. U.S. Pat. Off. s> K'*> So f% ni n o tp <T o 5* % 5' O The Information contained In this bulletin Si. to our belt knowledge, true end Accurate, but ell recommendation! or luggeitioni ere made without guarantee, since the condition! of uie are beyond our control. The Momenta Chemical Company diielaimi any liability incurred in connection with the uie of theie date or tuggeiliont. Furthermore, nothing contained herein ihell be conttrued ei e recommendation to uie any product in conflict with eihting patent! covering any material or iti uie. 0508529 ___ ___________ 1 TOWOLDMON0034092 WATER_PCB-00018561 Some important applications for protective and decorative coatings plasticized with Aroclor compounds - - Wood and metal used in yachts, barges and other marine craft. Structural steel for bridges, buildings, roofs and power-lines. Structural materials at chemical plants, pulp and paper mills, textile mills, petroleum refineries and gas works for protection against acid fumes, alkalies and gas. Tank cars and other rolling stock and construc tion machinery for protection against corro sive materials and weathering. Equipment and stop-off lacquers used in elec troplating. Masonry floors and walls. Concrete swimming pools. Highway markings. Cable coatings requiring fire resistance, chemical resistance, and excellent electrical properties. Textile coatings resistant to chemicals, fire and water. -1 - 0S08S30 TOWOLDMON0034093 WATER_PCB-00018562 WATER_PCB-00018563 Naming (nd Preparation^ of Aroclor Compounds Aroclor 4465--a 60:40 mixture (biphenyl to terphenyl) with 65 per cent chlorination. Aroclor 2565--a 75:25 mixture (biphenyl to terphenyl) with 65 per cent chlorination. The physical properties of the Aroclor plasticizers vary gradually with the degree of chlorination. At low percentages of chlorine, such as Aroclor 1221 and 1232, the compounds are clear and very.fluid. At 42 per cent they resemble vegetable oil; at 48 per cent they thicken slightly and look more like a medium-grade mineral oil. At 54 per cent chlorine, the compounds are quite viscous; if a bottle containing them is turned upside down, the bubble rises slowly to the top. At higher percentages, the biphenyls become gumlike, and a fingerprint on the surface lasts several days. Then at 68 per cent chlorine, the. range is complete; Aroclor 1268 is a white powder. The terphenyls (Aroclor 5442 and 5460) are both yellowish solids; The gradual change in physical properties often allows a processor to select a plasticizer particularly suited for his operation. For example, if he wants to dry mix the plasticizer, Aroclor 1268 could be used. It melts at higher processing temperature and can act as a solvent-plasticizer, 0^08532 II TOWOLDMON0034095 WATER_PCB-00018564 Properties of Chlorinated Rubber "Parlon" is a mixture of two polymers with an average chlorine content of 67 per cent made by chlorin ating natural rubber. The typical properties of "Parlon" as given by the manufacturer, Hercules Powder Company, Wilmington, Delaware, are listed in Table I. Table ). Typical Properties of "Parlon" General Form as shipped...................................................................................... White, granular powder Color of film............................................................................................ Water white Odor............................................................................................................None Clarity of film..........................................................................................Good Taste.................................................................................. ........................None Moisture, per cent as shipped............. ..................................................0.5 maximum Physical Specific gravity......................................................................................... 1.64 Specific volume, as shipped, in cubic inches per pound....................... 16.9 Hulking value, gallons per pound......................................................... 0.0735 Index of refraction...................................................................................1.554 Chemical 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 Electrical (clear unplasticized film*) Specific surface resistance, ohtnsXlO10.................................................2,000 Dielectric strength, volts per mil (ASTM 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 Films used in tests were laid down from a toluene solution. 0^08633 TOWOLDMON0034096 WATER_PCB-00018565 Properties, cont'd. Mechanical (clear unplestlcized 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.... ..... 1.4X10'- Hardness, Sward index, per cent of glass........... .... 90 Note; Flexibility of "Parlon" film increases with viscosity >f "Parlon" used. 1,000-cp. 4,850 4,360 3.3 3.4 - - Thermal [clear unplasficized 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*) Effect of sunlight........................................................................... Discolors and embrittles Effect of aging............................................................................... Very slight Effect of hot water........................................................................Rlushes Effect of cold water...................................................................... None Moisture absorption (80c/c relalive humidity for 24 hours), per cent...................................................................................... 0.27 Moisture vapor permeability of 0.003-inch film (grams water/ square cenlimeter/0.01 centimeter/hour at 21C.).............0.2X10* Viscosity Types Viscosity Type 5 cp....... 10 cp....... 20 cp....... 125 cp....... 1,000 cp....... Table II. "Parlon" Viscosity Types Viscosity Range (centipoises) .... 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 below: Type Example of Use 5 cp. In printing inks and as a fortifier for alkyd resin enamels. 10 cp. Inhigh-solids finishes and as a fortifier for alkyd resin and oleoresinous varnishes and enamels. 20 cp. As a film-former in protective coalings and as a fortifier in enamels and varnishes. 125 cp. As a film-former in protective coatings, in paper lacquers, adhesives, and textile finishes. 1,000 cp. As a film-former in adhesives, textile finishes and other finishes where flexibility is important. Films used in tests were laid down from a toluene solution. ex c,ft 8 5`3** TOWOLDMON0034097 WATER_PCB-00018566 Solvent Compatibility ' Solvents and solvent mixtures suggested for use in preparing formulations with Aroclor and "Parlon" are given in Table III: Table III. Suggested Solvents for Compositions with Aroclor and "Parlon ' "Amsco Solv," B and E Amyl acetate Butyl acetate Carbon tetrachloride "Cellosolve" Diacetone alcohol Diethyl carbonate Ethyl acetate Ethylene dichloride Hi-FJash naphtha Methyl acetate Xylene 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" Formulations and Properties of Chlorinated Rubber Chlorinated Rubber Films Aroclor 1262 and 5460, resinous types, show good compatibility in chlorinated rubber films laid down from toluene solution containing 20 per cent of the plastic in ratios of 2:1 and 1:1 ("Parlon" to Aroclor). The plasticizer types, Aroclor 1242, 1254 and 3260, also show good compatibility. Formulations and properties of films derived from both resin- and plasticizer-type Aroclor are listed below'. Table IV. Formulations for Aroclor Resin Ingredient Parts by Weight "Parlon," ZO-cp........................ ................... 16 16 16 12 12 Aroclor 5460............................. ................... 8 ...........Dibutyl phthalate..................... - 8 8 12 12 4- - 3 Tung oil, Thermolyzed, 976 ... ................... - - 5 -- - Xylene or butyl acetate.......... .................... 76 72 71 76 73 12 12 3. 72. Table V. Formulations for Aroclor Plasticizer Ingredient "Parlon," 20-cp........................ .................... 20 Aroclor 1 254 or 1260 ............. ................... 4 Xylene....................................... .................... 76 Parts by Weight 20 7 73 20 20 70 Ife 05O8^3b TOWOLDMON0034098 WATER_PCB-00018567 Films cast from these lacquers show improved characteristics due to Aroclor. Some of their advantages are listed below: Adhesion Unplaslicized chlorinated rubber films have very poor adhesion. The lacquer film containing Aroclor 5460 gave good adhesion to aluminum, bare steel, primed steel, galvanized iron and "Transite" surfaces. Othep commercial resins, particularly oil-modified alkyd resins, gave better adhesion to glass, tin, copper, sealed wood and cellophane. The lacquer films plasticized with Aroclor 1254 or 1260 gave good adhesion to "Transite," cellophane, gal vanized iron and primed steel surfaces. Some of the other commercial plasticizers tested in similar films gave better adhesion to aluminum, tin, bare steel, copper and sealed wopd surfaces. Though compounds with an Aroclor alone possess pronounced adhesive qualities, better adhesion to all of the surfaces results if mixtures of Aroclor Or varied contents are used. Resistance to Aqueous Solutions Chlorinated rubber films with Aroclor 1254 or 1260 (plasticizers) and Aroclor 5460 (resin) show satisfac tory resistance to solutions of 10 per cent hydrochloric acid, S per cent sodium l^vclroxide, 5 per cent sodium chloride and water spot tests. Film Hardness Softer films were produced with Aroclor 5460 in ratios of 5:10 and 10:10 (Aroclor:"Var]on") than with other commercial resins in similar mixtures. Likewise, softer films result from Aroclor 1 254 or 1260 in ratios of 2:10 and 5:10 (zlror/or^Parlon") than with other commercial plasticizers at these concentrations. From these tests compounds with Aroclor are shown to have strong plasticizing action on chlorinated rubber. Cold-Check Resistance Aroclor 5460 is superior to phenol formaldehyde resin? in cold-check resistance imparted to chlorinated rubber films, but not as good as alkyds modified with long oil. Aroclor 1260 used as a plasticizer proved somewhat better than Aroclor 1254. Weather Resistance Pigmented chlorinated rubber finishes containing Aroclor have consistently withstood outdoor weather tests, but unpigmented finishes do not stand up well regardless of the resin or plasticizer used. Poor resistance to ultraviolet light is also a weakness of chlorinated rubber. Most pigments (except ultra marine blue) are usable with "Parlon" and are recommended if the coating is to be subjected to outdoor weather or ultraviolet light. However, pigment protection varies considerably. Inspection of alkyd enamels fortified with "Parlon" showed weatherability varied from 63 months with chrome green to 4 months for titanium dioxide- iron blue combinations. Sanding and Polishing Properties Plastic films compounded with "Parlon" and containing Aroclor 5460, 1254 and 1260 have shown satisfac tory sanding and polishing characteristics. < 1 - 7- 0*08*36 TOWOLDMON0034099 WATER_PCB-00018568 Alkaline-Resistant Coatings Applications Products containing Aroclor and chlorinated rubber arc highly resistant to alkalies and moisture. Paints with combinations of Aroclor and chlorinated rubber are used in large quantities for concrete floors, walls, swimming pools and other surfaces. A paint formulation is given in Table VI. Table VI. Paint Formulation for Alkaline Surface (Peris by Weight) Ingredient Formulation Formula I (basement floors) Formula 2 (Fed. Spec. TT-Mi) "Parlon," 20-cp. type............ Aroclor 1254........................... "Rezyl 869"............................ 18 18 10 10 Aroclor 5460 or "Cumar Pl( "Bcckosol 31"......................... Tung oil, Thcrmolyzed, 976.. Titanium dioxide..................... Zinc oxide................................ Silica flour......... Carbon black........................... Xylene...................................... Hi-Flash naptha...................... 16 16 22 3 0.2 0.5 42.8 47.5 Totals......................... 100 100 Formula 3 (swimming pools) 14 6 4.4 2.9 4.4 19.7 6.5 47.5 100 Chemical-Resistant Finishes Particular care is necessary in choosing resins and plasticizers for chemical-resistant paints. Chlorinated rub ber formulations with an Aroclor have proved outstanding for acid and alkali resistance. Five formulations are shown in Table VII. Ingredient "Parlon," 20-cp. type.. Aroclor 5460................. `iiakelito XJ-12895",... ` Rezyl 807" (solids).,., Aroclor 1254................ Aroclor 1260................ Iron oxide.............. Titanium dioxide ... Zinc oxide.............. Zylene...................... Hi-Klash naphtha.. Toluene................... Formulations for Chemical-Resistant Paints (Ports by Weight) 1 Interior use, acids and eltslies . 16 . 6.4 .-- . .8 .-- .-- . 16 -- . . 53.6 .-- .-- . 100 2 Exterior use, acid* 16 -- -- 6.4 4.8 -- 4.8 16 -- -- 52 -- 100 Formulation 3 Exterior use, alkalies 16 6.4 -- 4.8 -- 4.8 16 -- -- 52 -- -- 100 4 Maximum resistance, alkalies 18 -- ... -- 8 6 -- 18 -- -- 39 11 -- 100 5 Soap resistant 12 6 -- -- --. 7.7 -- 18 6 28 10.3 12 100 0^0 TOWOLDMON0034100 WATER_PCB-00018569 ..-----V'.--.- -- ==-.--T --~ = These formulations were applied to metal bars or panels and tested for resistance. Formula I showed good resistance to 10 per cent hydrochloric acid and 5 per cent sodium hydroxide solutions. Formula 2 gave excellent outdoor protection to metal surfaces on plants manufacturing acids. Formula 3 performed well on exteriors of plants producing alkali. Formula A had excellent resistance to acids, alkalis and salt solutions. It also showed good adhesion to glass and other surfaces. Formula 5 proved good for resistance to warm, soapy water. Note: No finishes with Aroclor or chlorinated rubber are recommended for con tinuous exposure at temperatures above 140 I\ Marine Finishes The marine industry makes great use of chlorinated rubber coatings plasticized with Aroclor to protect wood and metal on boats, barges and other marine equipment. They possess good resistance to salt water and their hard finish deters algae and other marine growth. A suggested formula for a while marine paint is given in Table Vlll. Table Vlll. Formulation for a Chlorinated Rubber Marine Paint Ingredient Parts by Weight "Parlon," 20-cp. type............................................................ 20 Aroclor 1254.......................................................................... 6 "Rezyl 869"........................................................................... 6 Titanium dioxide................................................................... 25 Xylene..................................................................................... 23 Hi-Flash naphtha.................................................................. 20 Total.......................................................................... 100 Emulsion Paints If chemical resistance is required on porous surfaces, Aroclor 1254 is often added to chlorinated rubber emulsion paints. The Hercules Powder Company reports that preferred water phases for such paints are either a 1 per cent distilled water solution of "Aerosol OT" or a 4 per cent distilled-water solution of sodium oleate. A lacqucr-to-water ratio of 2.5 to 1 (by weight) is suggested for the complete emulsion "Parlon" of any viscosity may be used. A typical paint phase for such an emulsion paint is given in Table IX. i ___________________II TOWOLDMON0034101 WATER_PCB-00018570 Table IX. Formulation tor Paint Phase ot Emulsion -Paint Ingredient Parts by Weight "Parlon"................................................................................. 28 Aroclor 1254.............. 14 "Cumar PlO".............................................................. 10 Xylene..................................................................................... 24 Hi-Flash naphtha.................................................................. 24 Total.......................................................................... 100 Adhesives Chlorinated rubber adhesives with an Aroclor were developed originally for adhering labels to acid bottles because of their general resistance to chemicals. These adhesives are also of unusual interest because they are fire resistant. A typical formulation is given in Table X. Table X. Formulation for Chlorinated Rubber Adhesive Ingredient Parts by Weight "Parlon," 125-cp. type......................................................... Aroclor 1254.......................................................................... Aroclor 1260.......................................................................... Toluene................................................................................... Total......................................................................... 20 6 6 68 100 Paper and Textile Coatings Chlorinated rubber coatings with Aroclor are worthy of consideration for specific end uses in the paper and textile coating fields. In general, this type of coating is restricted by odor and taste. Unpigmented fin ishes seem suitable for certain fabrics used indoors, but not for exposure to high temperatures or direct sunlight. Electrical Coatings because of their desirable electrical properties, these compositions are useful for insulating and protecting electrical wire and apparatus from moisture. With selected fungistats and waxes, coatings of this type are used to protect electronic equipment in the tropics against moisture and fungi. The fire resistance of these plastics is an added dividend in the electrical field. Printing Inks Printing inks requiring a fast drying time and chemical resistance are often based on chlorihated rubber compositions plasticized with an Aroclor. These inks are especially useful on soap wrappers and boxes, bottle labels and many other commodities because of their alkali resistance. 0506539 TOWOLDMON0034102 WATER_PCB-00018571 Other Resins and Plasticizers Compatible With Chlorinated Rubbei The resins and Monsanto plasticizers given in Tables XI and XII are compatible with chlorinated rubber, but none gives the over-all desired qualities attained by using an Aroclor. The strong points and limitations of each arc known. If their use is necessary for specific applications in chlorinated rubber, more detailed in formation on them may readily be found. Table XI. Resins Compatible with "Parlon" "Ambcrol 801, 806P, ST-137, F7" Aroclor 1262, 5460 "Aroplaz 920, 930, 935, 940" "liakelite" XR-3180, XR-4503, XR-4006, UR-2963, XJ-9868, BR-1329, BR-3360" "Beckacite 1112" "Beckamine P-138, P-254" "Supcr-Bcckamine 3501" "Beckapol 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-61, D-62, E-71, 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 21., 28, 33" Methyl methacrylate polymers "Neville R-3, R-10" "Pentalyn A, G, M, X" `Tetrex 1, BOH" "Phenac 633-M" "Rezyl 1 16, X315, 412, 775, 803, 807, 829, 869, 880, 1103" Rosin Santolitc* MPH (sulfonamide-aldehyde resin) "Stabelite Ester 1, 2, 10" "Stabelite" resin "Super-Beckacitc 1001" "Syntex HI, H3, H12, 17, 213, 22, 28, 29, 32, 36" "Teglac 15, Z-1S2" "Yelsicol AD6-3" "Vinsol" Table XII. Monsanto PUsticliers Compatible with "Parlon" Aroclor 1242 Aroclor 1254 Aroclor 1260 Dibutyl phthalate Diethyl phthalate Dimethyl phthalate Santicizcr B-16 (butyl phthalyl butyl glycolalc) Santicizcr M-l7 (methyl phthalyl ethyl glycolate) Tricresyl phosphate Triphenyl phosphate Sanrolitf, Sorttimer; Monsanto Trademaiks. Reg. U.S. Pat Off. -11- 0500**0 TOWOLDMON0034103 WATER_PCB-00018572 Toxicity Animal toxicity studies and 20 years of manufacturing and use experience indicate that Aroclur compounds are not serious industrial health hazards. If the materials are heated to volatilization, ventilation should be provided to prevent inhalation of vapors. This is true of other major components of the formulation as well as the Aroclor compounds. Repealed or prolonged skin contact should be avoided although there are few instances of skin irritation. Human patch tests with finished products containing Aroclor compounds have shown no irritation. Mon santo will furnish information on specific Aroclor compounds upon request. Shipping Information Regulations Standard Containers - - None -- Steel and Fiber (Aroclor 1268, 5460) drums, Rail Classification Chlorinated diphenyl (synthetic resin, liquid, NOIBN) Synthetic resin, liquid, NOIBN Snythetic resin, other than liquid, NOIBN --Aroclor 1142, 1148, 1154, 1160, 1162, 1168, 1221, 1232, 1242, 1248, 1254, 1260,1268 -- Aroclor 1260 mix, 1262 mix -- Aroclor 2565, 4065, 4465, 5042, 5060, 5442, 5460 . Truck Classification Synthetic resin powder, NOI Synthetic resin, lumps or'solid mass, NOI --- Aroclor 2565 --Aroclor 4065, 4465, 5042, 5060, 5442, 5460 -12- 0*00541 TOWOLDMON0034104 WATER_PCB-00018573 Trademark Index Trademark Company "Aerosol OT" "Amberol" "Amsco Solv" "Aroplaz" "Bakelite" "Beckacite" "Beckamine" "Beckopol" "Beckosol" "Beetle" Resin "Cellosolve" "Clorafin" "Cumar" "Duraplex" "Esterol" "Formvar" "Gelva" "Glyptal" "Hercolyn" American Cyanatnid Company Rohm & Haas Company American Mineral Spirits Co. U. S. Industrial Chemicals Co. Bakelile Company Reichhold Chemicals, Inc. Reichhold Chemicals, Inc. Reichhold Chemicals, Inc. Reichhold Chemicals, Inc. American Cyanamid Company Carbide & Carbon Chem. Co. Hercules Powder Company Barrett Division, Allied Chem. & Dye Rohm & Haas Company L. Sonnebom Sons, Inc. Shawinigan Resins Corp. Shawinigan Resins Corp. General Electric Company Hercules Powder Company "Lewisol" "Neville" "Penlalyn" "Petrex" "Phenac" "Rezyl" "Solvasol" "Solvesso" "Stabelile" Ester "Stabelite" Resin "Super-Beckacite" "Syntex" "Teglac" "Tollac" "Troluoil" "Transite" "Velsicol" "Vinsol" Hercules Powder Company Neville Chemical Company Hercules Powder Company Hercules Powder Company American Cyanamid Company American Cyanamid Company Socony-Mobil Oil Company Esso Standard Oil Hercules Powder Company Hercules Powder Company Reichhold Chemicals, Inc. Flintkote Company American Cyanamid Company Neville Chemical Company Anderson-Pritchard Oil Corp. Johns-Manville Sales Corp. Velsicol Corp. Hercules Powder Company m v- I rh/POB--2M---148 Rw.WWiJRC 1/61 lVfcM -13- PrlnUd In U.8.A. OS085<i2 TOWOLDMON0034105 WATER_PCB-00018574 /-- Monsanto U ft' ^ S'" ao r- 7e9 or ir For furthei information on the products described in this bulletin contact the nearest Monsanto office. MONSANTO CHEMICAL COMPANY ST. LOUIS, MISSOURI AKRON ATLANTA BOSTON CHICAGO CINCINNATI CLEVELAND DETROIT HOUSTON LOS ANGELES MINNEAPOLIS NEW YORK SAN FRANCISCO SEATTLE WILMINGTON MONSANTO CHEMICALS LTD. London MONSANTO CHEMICALS (AUSTRALIA) LTD. Melbourne MONSANTO (CANADA) LTD. Montreal Toronto Vancouver SS iI TOWOLDMON0034106 WATER_PCB-00018575