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TE C H N I CAL BULLET AROCLOr PLASTICIZERS A series of inert, chemically-resistant, fire-retarding plasticizers compatible with wide variety of resins. TECHNICAL BULLETIN 0/PL-306A Monsanto OA317J8 TOWOLDMONOQ32099 AROCLOR PLASTICIZERS A series of inert, chemicalfy-resistant, fire-retarding plasticizers compatible with wide variety of resins. TECHNICAL BULLETIN 0/PL-306A CAUTION : see sections entitled Toxicity and Safe Handling, and Environmental Hazzards, on page 12. "Nothing ttmlained herein is lo be construed as a recommendation to many pTodud in conflict with any patent MONSANTO MAKCS NO WARRANTIES AS TO THE FITNESS OR MERCHANTABILITY OF ANY PRODUCTS REFERRED TO. no guarantee of salnlKlory results horn reliance upon con tained information 01 recommeridel ions, and disclaims all liability foi any resulting loss or damage " Organic Chemicals Division/8D0 N. Lindbergh Blvd./St. Louis, Missouri 63166 0431739 TOWOLDMONOQ32100 Introduction The unique Aroclor plasticizers are among the most versatile chemi cally produced materials available. One outstanding characteristic -- inertness -- makes Aroclor useful in many ways for many different applications. The major benefits offered by Aroclor include: Chemical Resistance Fire Retardance Compatibility with most resins Nonoxidation Adhesivity Low Cost Solubility Monsanto's Aroclor plasticizers comprise a series of chlorinated bi phenyls and chlorinated polyphenyls. They vary from mobile, oily liquids to white crystals and hard, transparent resins. Twelve of the Aroclor plasticizers, each of which represents a series, are discussed in this bulletin. An understanding of the system for designation of each Aroclor should prove useful in the evaluation of the property gradations among them. The last two digits indicate the approximate weight percentage of chlorine in the product, and the first two digits indicate the type of material, as follows: 12 -- chlorinated biphenyls 25 -- blend of chlorinated biphenyls and chlorinated triphenyls (75:25) 44 -- blend of chlorinated biphenyls and chlorinated triphenyls (60:40) 54 -- chlorinated triphenyls For nearly every Aroclor mentioned, a darker, less-pure grade exists, with about the same physical and chemical characteristics, but lower in price. ________________ _ The Aroclor liquids and resins are readily soluble in most common organic solvents and drying oils. Although all Aroclor plasticizers are insoluble in water, the hard, crystalline materials are generally less soluble than the liquids and softer resins. Solubilities of some Aroclor plasticizers are shown in Table 1. 04317<tO 3 TOWOLDMONOQ32101 TABLE 1 SOLUBILITIES OF AROCLOR PLASTICIZERS IN VARIOUS SOLVENTS Solvent Acid Acetic Acid Oleic Acid Benzoic Acid Arcelor 1242 25C Hot S S io.o31^ s s -- Aroclor 1248 25C Hot _ -- 10.032c _ -- -- Aroclor 1254 25C Hot Ss Ss ---- Aroclor 1268 Cold Hot __ ---- ---- Aldehyde 40% Formaldehyde Furfural 1I111111 vs vs vs vs VS vs ss ss Amine Aniline Pyridine s 132.530OC s 44Q9S-C -- ss -- 11431c 425100X -- -- Chloro derivatives Amyl chlorides -- mixed s s s s S s Carbon Tetrachloride S s s s s s ---- Chloroform Ssssssss Dichlorethylene -- -- -- ---- -- -- -- Ethylene Dichloride s s s s s s s s Monochlorobenzene s s s s s s ---- Orthodichlorobenzene -- -- -- -- -- -- -- -- Tetrachlorethane s s s s s s ---- Trichlorethane s s s s s $ ---- Trichlorethylene s s s s s s ---- Drying Oil Tung Oil Linseed Oil ssssss ssssss 1 s Ester Amy! Acetate ssssssss Butyl Acetate ssssssss "Cellosolve"* Acetate s s s s s s ---- Cottonseed Oil s s s s s s ---- Dibutyl Phthalate ssssssss Aroclor 446 Cold l SS S -- I VS vs vs VS vs VS vs vs vs vs vs vs vs vs vs vs vs vs s s TVZTEVO TOWOLDMONOQ32102 Diethyl Phthalate S s s s s s ---- s Ethyl Acetate S s s s s s ss ss s Ethyl Lactate S s s s s s 1 s vs Ethylene Glycol Diacetate s s s s s s -- -- vs Methyl Acetate s s s s s s ss ss s Tricresyl Phosphate s s s s s s -- -- ss Ether: Ethyl Ether ssssss ss s Ether Alcohol Carbitot' 2243,c 30739C vs vs 17326-C 2S9S8C 1 s ss Ceffosofre SSssss 1 ss Diethylene Glycol ---------------- s prp'-Dihydroxy Ethyl Ether 16,923c 1999C ss ss g30C igiooc -- -- ss Hydrocarbon Benzene Gasoline Kerosene Mineral Spirits Paraffin Pine Oil Toluene Turpentine Xylene VS vs vs vs vs vs s s vs vs vs vs vs vs vs -- -- vs vs vs vs vs vs vs ss s vs vs vs vs vs vs vs s s vs 2_027.5C s 2.o?8',c s -- s -- -- 5.0 s s vs vs s s s s s vs vs vs vs vs vs s s vs vs vs vs vs vs vs s s vs vs vs vs vs vs vs s s vs Hydroxy derivatives Amyl Alcohol /r-Butyl Alcohol Ethyl Alcohol (3-A) Glycerine Methyl Alcohol Phenol - 90% Ketone: Acetone s s 23.32c 1 42.529c 19430t S s s eo.o70^ i sas60"1 s s -- -- -- 1 -- -- -- -- s s ss --s s 1 -- 1027*C 2875c 1 1111 -- 15C 22.26SOC -- -- ss s ss --s s 1 s ss 1 1 -- s 1 s ss ss 1 ss s s Miscellaneous Carbon Disulfide Nitrobenzene Water S s -- -- s s s s vs s s -- -- s s -- -- vs 1 1 11 11 111 I -- Insoluble SS -- Slightly Soluble S -- Soluble VS -- Very Soluble. Figures show grams of Aroclor per 100 milliliters of solvent at 25C unless otherwise indicated. *Tratf*nritof \Mign CrM Cwpu CP TOWOLDMONOQ32103 TABLE 2 CHEMICAL AND PHYSICAL PROPERTIES OF REPRESENTATIVE AROCLOR PLASTICIZERS AND RESINS Property Appearance Aroclor 1221 Clear, mobile oil Aroclor 1232 Clear, mobile oil Aroclor 1242 Clear, mobile oil Aroclor 1248 Clear, mobile oil Aroclor 1254 Light-yellow viscous liquid Color, maximum *100 APHA *100 APHA *100 APHA *100 APHA *100 APHA Chlorine, percent 20.6-21.5 Acidity, mg KOH/g. maximum *0.014 Moisture, ppm, maximum - Ave, Coefficient of Expansion, cc/cc/'C 0.00071 (15*-40*C) Specific Gravity *1.182-1.192 (25715.6"C) Density, pounds per gallon, 25C 9.85 Distillation Range, *C, corrected (ASTM D-20, modified) 275-320 Evaporation Loss, %, 100*C, 6 hours (ASTM D-6, mod.) 163C, 5 hours 1.0-1.5 Flash Point (Cleveland Open Cup), *C 141-150 *F 286-302 Fire Point (Cleveland Open Cup), "C 176 F 349 Pour Point (ASTM E-97), *C 1 (crystals) F 34 (crystals) Softening Point (ASTM E-28), *C *F Refractive Index, n 0*20 20C 1.617-1.618 Viscosity, Seconds Saybolt Universal (ASTM D-88) 100F (37.8*C) 130F (54.4*C) 210F (98.9C) *38-41 36-37 30-31 Monunto Sp*ctfic*tk>ni 31.5-32.6 *0.014 - 0.00073 (25*-100C) *1.270-1.280 (25715.5'C) 10.55 290-325 1.0-1.5 152-154 305-310 238 460 -35.5 -32 - 1,620-1.622 *44-51 39-41 31-32 42 *0.015 *50 0.00068 (25-65*C) *1.381-1.392 (25715.5"C) 11.50 325-366 0-0,4 3.0-3.6 176-180 348-356 None to boiling point -19 2 -- 1.627-1.629 *82-92 49-56 34-35 48 *0.010 *50 0.00070 (25-65C) *1.405-1.415 (65715.5*0 12.04 340-375 0-0,3 3.0-4.0 193-196 379-384 None to boiling point -7 19.4 - 1.630-1.631 185-240 *73-80 36-37 54 *0.010 *50 0.00066 (25-65C) *1.495-1.505 (65715.5"C) 12.82 365-390 0-0.2 1.1-1.3 None to boiling point None to boiling point 10 50 - 1.639-1.641 1800-2500 260-340 *44-48 0431743 TOWOLDMONOQ32104 Aroclor 1260 Light-yellow. soft. sticky resin *150 APHA 60 *0.014 *50 0.00067 (20*-100C) *1.555-1.566 (90715.5`C) 13.50 385-420 0-0.1 0.5-0.B None to boiling point None to boiling point 31 88 1.647-1.649 Aroclor 1262 Aroclor 6442 Light-yellow sticky, viscous resin Clear yellow sticky resin *150 APHA *2 NPA (molten) 61.5-62.5 42 *0.014 0.05 - 0.00064 (25"-65"C) - 0.00123 (25*-99*C) *1.572-1.583 (90715.5*0 1.470 (26725*0 13.72 12.24 390-425 215-300 (4 mm. Hg) 0-0.1 0.5-0.6 0.01 0.2 None to boiling point 247 477 None to boiling point >350 >662 38-38 99 46 115 *46-52 115-126 1,6501-1.6517 - Aroclor 4466 Clear, light-yellow. resin *2 NPA (molten) 65 0.05 - 0.00061 (26-65*C) 1.670 (25725'C) 13.91 230-320 (4 mm. Hg) 0-0.02 0.2-0.3 None to boiling point None to boiling point ___ *60-66 140-151 1.664-1.667 Aroclor 2666 Aroclor 6460 Aroclor 1268 Black, opaque. brittle resin Clear, yellowto-amber. brittle resin or flakes White to off-white powder *2 NPA (molten) *1.5 NPA (molten) 65 58.5-60.6 68 1.4 0.05 0.05 - 0.00066 (25-65C) - 0.00179 (25*-124*C) - 0.00067 (20'-100*C) 1.734 (25725'C) 1.670 (25*/25*C) 1.804-1.811 (25725*C) 14.44 13.91 15.09 280-335 (5 mm. Hg) 435-450 0.2-0.3 __ 0.03 None to boiling point 0-0.06 0.1-0.2 None to boiling point None to boiling point None to boiling point . *66-72 149-162 - *98-105 208-222 1.660-1.665 *150-170 (hold 302-338 point) - 600-850 3200-4500 (160"F; 71*C) 90-150 -- -- -- *72-78 *86-100 300-400 (266'F; 130C) M&nunto SptclfcrtloM. TOWOLDMONOQ32105 Density All the Aroclor plasticizers are heavier than water, a valuable property for many applications. Densities are shown in Figure 1. 0 40 80 120 160 200 240 2S0 320 360 400 440 480 Temperature, C Fig. 1 -- Densities of Aroclor Plasticizers at Various Temperatures 0 Specific Volume The specific volume of Aroclor 1248 at different temperatures is as follows: Temperature (f) 0 100 200 300 400 500 600 Aroclor 1248 Specific Volume (mljgj 0.674 0.699 0.726 0,755 0.790 0.828 0.870 043174& TOWOLDMONOQ32106 Volatility The low vaporization loss of Arodor plasticizers is indicated in Table 3. TABLE 3 VAPORIZATION RATES OF AROCLOR PLASTICIZERS Plasticizer (Surface area: 11.28 sq. cm.) Aroclor 1221 Aroclor 1232 Wt. loss (g) 0.5125 0.2572 Exposure at 100C (hr.) 24 24 Vaporization Rate (glsq. cm.lhr 0.00174 0.000874 Aroclor 1242 0.0995 24 0.000338 Aroclor 1248 Clorafin"-42-S 0.0448 0.0745 24 48 0.000152 0.000126 Dioctyl phthalate 0.0686 48 0.000117 Dutrex** 25 0.0256 24 0.000087 Aroclor 1254 0.0156 24 0.000053 Shell Dutrex 20 0.0047 24 0.000016 Aroclor 1262 Aroclor 1260 0.0039 0.0026 24 24 0.000013 0.000009 Aroclor 4465 0.0064 72 0.000007 Aroclor 5442 Aroclor 5460 Tricresyl phosphate 0.0039 0.0032 0.0010 72 72 24 0.000004 0.000004 0.000003 It is concluded that the vaporization rates of Aroclor plasticizers -- especially the most widely used 1254 and 1260 -- compare most favorably with the similar constants of other plasticizers selected specifically for these tests because of their low vaporization rates. *Td*mirk H*rcul**,lnc. of lOil Ct. 04317*6 9 TOWOLDMONOQ32107 Vapor Pressure The vapor pressures of several -Arodor plasticizers are indicated in Figure 2 over the temperature range 150 to 300C. Temperature, C Fig. 2 -- Vapor Pressures of Aroclor Plasticizers The estimated vapor pressures of several Aroclor plasticizers at 100F shown in the following table were determined by extrapolation from the values shown in Figure 2. Approximate Vapor Pressure of Aroclor Plasticizers Estimated at 100 F (37.8 Cj Aroclor 1232 0.005 mm. Hg Aroclor 1242 0.001 mm. Hg Aroclor 1248 0.00037 mm. Hg Aroclor 1254 0.00006 mm. Hg <H317*7 TOWOLDMONOQ32108 Viscosity The viscosities of the Aroclor plasticizers vary according to whether the base material is a biphenyl or a polyphenyl and on the degree of chlorination. In general the low-chlorinated biphenyls have the lowest viscosities (Figure 3). TOWOLDMONOQ32109 Toxicity And Safo Handling Inhalation At ordinary temperatures the Aroclor chlorinated polyphenyls have not presented industrial toxicological problems. The hazard of potential toxic exposure varies with their volatility: the lower-chlorinated, morevolatile ones present more of a potential problem from the standpoint of both inhalation and skin contact. When Aroclor plasticizers are used at elevated temperatures, engineering controls must be applied, either by the use of closed systems or by effective local-exhaust ventilation together with general workroom exhaust. Vapor of the liquid Aroclor plasticizers at room temperature should not be breathed in a confined space, and no vapor of any Aroclor evolved at elevated temperatures should be allowed to be dispersed into the general workroom. Inhalation teste on animals indicate that the maximum safe concen tration of vapor is in the range of from 0.5 to 1.0 milligram of the lower-chlorinated Aroclor plasticizers per cubic meter of air. The threshold limit values (maximum allowable concentration for an 8hour working day) set by the American Conference of Government Hygienists are 1.0 milligram of the lower-chlorinated Aroclor com pounds per cubic meter of air and 0.5 milligram of the more-highlychlorinated compounds, such as Aroclor 1254, per cubic meter of air. Skin Contact Schwartz patch tests on 200 volunteers showed that Aroclor 1254 was neither a primary skin irritant or a sensitizer. Prolonged or repeated skin contact with the Aroclor plasticizers must be avoided by the use of gloves and protective garments, because of the possible occurrence of a condition called chloracne. Although re ports of this condition caused by Aroclor are rare, it can be produced by excessive skin contact. If any Aroclor is spilled on the skin the skin should be washed in the usual manner with a soap solution. A bum caused by contact with a hot Aroclor should be treated like any ordinary bum. Aroclor plasticizer adhering to the burned area need not be removed immediately, unless treatment of the bum demands it, in which case either soap and water or repeated washings with a vegetable oil are recommended. t 0*i 31 7*t9 12 TOWOLDMONOQ32110 Environmental Hazards Aroclor 1232, Aroelor 1242, Aroclor 1248, Aroelor 1254, Aroclor 1260, Aroclor 1262, Aroelor 1268, Aroclor 4465, and Montar 1 all contain polychlorinated biphenyls (PCB) of various types and in varying amounts. PCB residues in small amounts have been found in the environment and some studies have indicated that they may be harmful to certain forms of animal life. Extreme care should therefore be taken by all users of PCB-containing products to prevent any entry into the environment through spills, leakage, use, disposal, vaporization or otherwise. Further, the products in which PCB materials are used, or which are formulated using PCB materials as a component, should be given careful study to eliminate the possibility that PCB might reach the environment as a result of use in a given application. Some specific applications where the use of PCB should definitely be avoided are in paints and sealants for swimming pools, paints and waterproofing agents in silos and other buildings where food products for humans or animals are stored, and as a component of any container or wrapping used in the packaging of food products. 0431750 13 TOWOLDMONOQ32111 * Shipping Freight Classification Aroclor 1221, 1232, 1242, Synthetic Resin, Liquid, NOIBN 1248,1254, 1260, 1262 Rail Classification Aroclor 1268, 4465, 5442, 5460 Synthetic Resin, Other Than Liquid, NOIBN Truck Classification Aroclor 1268 Aroclor 4465, 5442, 5460 Synthetic Resin, Powder, NOI Synthetic Resin, Lumps or Solid Mass, NOI Shipping Regulations None Standard Containers Aroclor 1221 Aroclor 1232 Aroclor 1242, 1248, 1254, 1260, 1262 Aroclor 1268 Aroclor 4465 Aroclor 5442 Aroclor 5460 (flaked) Tank car, 520-lb. steel drum, 50-lb. can Tank car, 550-lb. steel drum, 50-lb. can Tank car, 600-lb. steel drum, 50-lb. can 200-lb. fiber drum, 25-lb. fiber drum 500-lb. steel drum, 50-lb. can 450-lb. steel drum, 50-lb. can 50-lb. bag 0431751 14 TOWOLDMONOQ32112 0431751.0] 15 TOWOLDMONOQ32113 SfOmsd' DISTRICT SALES OFFICES ALL DIVISIONS AKRON, OHIO 44313 260 Springside Drive Montrose Development Park Jet. (216) 666-4111 ATLANTA, GEORGIA 30326 Lenox Towers East 3400 Peachtree Rd. N. E. -- Suite 1711 Tel. (404) 577-2260 BOSTON, MASSACHUSETTS 02149 Everett Station Tel. (617) 387-5010 CHICAGO, ILLINOIS 3158 Des Plaines Ave. Des Plaines, Illinois 60018 Tel. (312) 296-6688 CINCINNATI, OHIO 45206 1501 Madison Road Tel. (513) 751-6707 DETROIT, MICHIGAN 500 Northland Towers West Southfield, Mich. 48075 Tel. (313) 357-0910 HONOLULU, HAWAII 96812 205 Pacific International Bldg. 677 Ala Moana B/vd., P. O. Box 3824 Tel (808) 531-2744 HOUSTON, TEXAS 77027 1301 Post Oak Tower 5051 Westheimer Road Tel. (713) 621-9550 LOS ANGELES, CALIFORNIA 90022 6670 E. Flotilla St. Tet. (213) 723-2492 NEW YORK, NEW YORK 10017 277 Park Avenue Tel. (212)922-4111 ST. LOUIS, MISSOURI 63166 800 N. Lindbergh Btvd. Tel. (314) 694-1000 SAN FRANCISCO BAY AREA 2710 Lafayette, Santa Clara, Calif. 95052 Tel. (408) 243-0414 SEATTLE, WASHINGTON 98121 2112 Third Avenue Tet. 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(319) 263-1331 Hydrocarbons & Polymers Division NEW ENGLAND AREA 730 Worcester St, Indian Orchard, Mass. 01051 Tel. (413) 788-6911 Lion OH EL DORADO, ARKANSAS 71730 Lion Oil Building Tel. (601) 863-3111 JACKSON, MISSISSIPPI 39209 P. 0. Box 10937, Westland Station Tet. (601) 362-3646 N. LITTLE ROCK, ARKANSAS 72119 410 West 8th Street, P. 0. Box 5621 Tel. (601) 376-2437 MEMPHIS, TENNESSEE 38113 1023 Riverside Drive, P. 0. Box 13248 Tel. (901) 848-4451 Plastic Products & Resins Division EUGENE, OREGON 97402 865 Seneca Road Tel. (603) 342-7201 KENILWORTH, NEW JERSEY 07033 North Seventh St. & Monroe Ave. Tel. (201) 276-2900 SPRINGFIELD, MASS.01101 P.O.Box 2130, Tel. (413) 788-6911 Textiles Division ATLANTA, GEORGIA 30303 Atlanta Merchandise Marl 240 Peachtree St., N. W. Tel. (404) 677-2260 CHARLOTTE, NORTH CAROLINA 28210 6230 Fairview Road. Suite 400 Tel. (704) 364-0110 GREENVILLE, SOUTH CAROLINA 29606 McAlister Plaza P. 0. Box 6664, Station B Tel. (803) 239-9171 NEW YORK, NEW YORK 10001 350 fifth Ave. Tel. (212) 556 5100 MONSANTO, 800 N. LINDBERGH BLVD., ST. LOUIS. MISSOURI 63166 3/70 J 0431752 P.3r>Q?.nR7fJ fi MTwft IN IJ.S A % TOWOLDMONOQ32114 Monsanto BOO H. LINDBERGH BLVD., ST. LOUIS. MISSOURI S31B6 TOWOLDMONOQ32115