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/I/ o ' AROCLOR resins and plasticizers for chlorinated rubber TECHNICAL BULLETIN No.PL-311 JANUARY,1958 / Monsanto _.VI_ DSW 323349 STLCOPCB4074997 aaaaij^^.v si This bulletin replaces Monsanto'Technical Bulletin No. 0-124 dated May. 1957. ! I I oS\N 32^50 STLCOPCB4074998 Some important applications tor 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 construction machinery for protecting against corrosive materials and weathering. Equipment and stop-off lacquers used in electroplating. 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. DSW 323351 1 STLCOPCB4074999 ir -ilnrn'T--irrr '-rivMiiiini4rW-^ ~~-'~f^TraM~"''-WrvT^ . --i TABLE OF CONTENTS Pago Naming of Aroclor Compounds.--------------- ------------------------------------------------------ 3 Properties of Chlorinated Rubber '_ General:----------------------------------- ------------------------------------------------------------ 4 Physical4 ____ Chemical Resistance..____ .________ ---------------- --- .--------- 4- _ Electrical4 Mechanical5 Thermal__ ...____________ ------- .-I -- ----------------- ----------------------------5 Physical-Chemical5 Viscosity Types____________________________________ ____________________________ 5 Solvent Compatibility.__ _."I.1 ------------------------------------------- 6 Formulation and Properties of Chlorinated Rubber .-Formulation for Aroclor Resins_________________ ______ _______.1-------- - (> " Formulation for Aroclor Plasticizers6 Properties of Formulated Films 7 Applications -'^Alkaline-Resistant Coatings.---------- --------- - -- ----------- 8 Chemical-Resistant Finishes-------------------- ----------------------------------------------- 8 Marine Finishes9 Emulsion Paints9 -=. Adhesives__ __________________ _____ .-------------------- ________ 10 Paper and Textile Coatings10 Electrical Coatings10 Printing Inks10 Resins for Chlorinated RubberII Monsanto Plasticizers for Chlorinated Rubber.II Toxicity12 Shipping Information___________________________________________________________ 12 Trademark Index13 D DSW 323352 L/ 2 STLCOPCB4075000 9 ' - '^ . AROCLOR* J - resins and plasticizers for chlorinated rubber .r.j INTRODUCTION Monsanto produces a series ol chlorinated biphenyls and polyphenyls identified by the trade mark 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 unusually good weatherability. Chlorinated rubber films plasticized with an Arodor grip common structural materials in strong adhesive bonds and the addition of an Arodor improves the flexibility and life of chlorinated rubber and plastic coatings. The formulations suggested in this bulletin are common in commercial practice today. They are given as a starting point or guide in developing formulations that expand the outstanding qualities of these compounds. Naming of Aroclor Compounds ' '" ~" The last two digits in a numbered series refer to the degree of chlorination by weight. Arodor 1248 is a biphenyl with 48 per cent chlorination. Arodor 5460 is a terphenyl with 60 per cent chlorination. Two special mixtures are: : ._ .......... . ____ _ Arodor 4465--a 60:40 mixture (biphenyl to terphenyl) with 65 per cent chlorination. Arodor 2565--a 75:25 mixture (biphenyl to terphenyl) with 65 per cent chlorination. The physical properties of the Arodor plasticizers vary gradually with the degree of chlorination. At low percentages of chlorine, such as Arodor 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; Arodor 1268 is a white powder. The terphenyls (Arodor 5442 and 5460) are both yellowish solids. O 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, Arodor 1268 could be used.It melts at higher processing temperature and can act as a solvent-plasticizer. *Aroclor: Monsanto Trademark, Reg. U.S. Pat. Off. 3 DSW 323353 STLCOPCB4075001 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 I. Typical Properties of 'Parlon'' General Form as shipped................ ................ ............................... _i..i..._....-.....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 Bulking value, gallons per pound.......................................... ........... ..0.0735 Index of refraction.................................................--....... --............... 1.554 Chemical resistance to: Acids, weak............................................................................................ .excellent f'i -- Acids, strong.............................. I.......................................................... excellent Alkalies, weak...................................... ...................... ---........... ...... ...excellent Alkalies, strong...........................,,.................. ..................... ................ .excellent Salt spray..................................................................... ..................... .....good Alcohols.................................................................................................. excellent Ketones..... ,,...... ,,............... ....................... ............. ..............................soluble Esters............................................................................... .......................soluble Hydrocarbons, aromatic............................................. ......... ................ .soluble Pydrocarbons, aliphatic........................................................................good Oils, mineral................................................................... ....................... good Oils, animal............ .................................. ............................................ poor Oils, vegetable................................................................ -............ ,........ poor Electrical (clear unplasticized film*) Specific surface resistance, ohmsXlO10...............................................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. DSW 323354 4 STLCOPCB4075002 ..^ ^^wgaiiaaa*-kA,v av, *&VJ w-Vrw?..f *r. ijSaaafiSa^afaaafeJ 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 I Ethyl acetate Ethylene dichloride Hi-Flash naphtha ' Methyl acetate Xylene Methyl ethyl ketone Methyl isobutyl ketone Methyl salicylate Notol - Octyl-acetate "SovasoF'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 1260, 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," 20-cp......................... .................. 16 16 16 12 12 Aroclor 5460.............................. .................. 8 8 8 12 12 Dibutyl phthalate....................................... .-- 4 ---- 3 Tung oil, Thermolyzed, 976 ... .................. -- -- 5---- Xylene or butyl acetate........... .................. 76 72 71 76 73 12 12 -- 3.75 72.25 - Table V. Formulations for Aroclor Plasticizer Ingredient "Parlon," 20-cp......................... ..................20 Aroclor 1254 or 1260.............. ..........:....... 4 Xylene........................................ ..................76 Parts by Weight 20 7 73 20 20 70 ) ! SW 323356 6 STLCOPCB4075003  1fI I i i s i .t :} .i ) i Films cast from these lacquers show improved characteristics due to Aroclor. Some of their advantages are listed below: ~' 7 Adhesion / _- Unplasticized chlorinated rubber films have very poor adhesion. The lacquer film containing Aroclor S460 gave good adhesion to aluminum, bare steel, primed steel, galvanized iron and `'Transite" surfaces. Othei* commercial resins, particularly oil-modified aikyd 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, 5 per cent sodium hydroxide, 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 (droc/or:"Parlon") than with other commercial resins in similar mixtures. Likewise, softer films result from Aroclor 1254 or 1260 in ,ratios of 2:10 and 5:10 (/lroc/or:"Parlon") than with other commercial plasticizers at these concentrations. r From these tests compounds withAroclor -are shown to have strong plasticizing action on chlorinated rubber. Cold-Check Resistance Aroclor 5460 is superior to phenol formaldehyde resins 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 aikyd 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. I osVJ 32W51 STLCOPCB4075004 ssm* ftiinranr- TFttiwi^nirrrriilirnrfftf'ir Applications Alkaline-Resistant Coatings Products containing Aroclor and chlorinated rubber are 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 j>aint formulation is given in Table VI. . Table VI. Paint Formulation for Alkaline Surface (Parts by Weight] Ingredient - Formulation Formula I (basamant floors) Formula 2 (Fed. Spec. TT-P-91 "Parlon," 20-cp. type................ 18 18 Aroclor 1254............................... 10 10 "Rezyl 869"............................... 8 Aroclor 5460 or ``Cumar P10". 6 "Beckosol 31"............................ Tung oil, Thermolyzed, 976..... Titanium dioxide........................ Zinc oxide.................................. Silica flour.................................. Carbon black.............................. Xylene......................................... - Hi-Flash naptha......................... Totals............................ 16 2 3 0.2 42.8 100 16 2 -- 0.5 47.5 100 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 anAroclor have proved outstanding for acid and alkali resistance. Five formulations are shown in Table VII. ~' Table VII. Formulations for Chemical-Resistant Paints ----- ^ (Parts by Weight) .. ... Ingredient .- . . : - - . - ^" ---- . .. 1 Interior use. acids and alkalies T- 2 Exterior use, acids Formulation 3 Exterior use, alkalies . 4 Maximum resistance, acids and alkalies "Parlon," 20-cp. type............. . Aroclor 5460................................. . "Bakelite XJ-12895"............... "Rezyl 807" (solids)............... . Aroclor 1254................................. . Aroclor 1260................................. . Tung oil, Thermolyzed, 976. . Iron oxide........................................ Titanium dioxide....................... . Zinc oxide............................. . Zylene.................................... Hi-Flash naphtha................ . ; : Toluene......................'...."....... , Totals....................... . 16 6.4 -- -- 8 ---- --' 16 ----53.6 -- --100 16 16 -- -- -- 6.4 6.4 ' -- 4.8 -- - 4.8 -- 4.8 4.8 16 -- --- . 52 -- --100 16 -- --- 52 ' '--- ------- 100 ' _ 18 -- -- -- 8 6 -- 18 -- -- 39 11 -- 100 5 Soap resistant 12 6 -- -- -- -- 7.7 -- 18 6 28 10.3 12 100 DSW 323358 8 ' 'i/.' STLCOPCB4075005 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 4 had excellent resistance to acids, alkalis and salt solutions. It also showed good adhesion to glass and other surfaces. ________ ^ :______ r 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 F. 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 white marine paint is given in Table VIII. ' Table VIII. Formulation for a Chlorinated Rubber Marine Faint __ Ingredient _ "Parlon," 20-cp. type. Aroclor 1254............... "Rezyl 869"............... . Titanium dioxide........ Xylene......................... . Hi-Flash naphtha....... Total.............. ^ , Parts by Weight 20 6 1. 6 25 23 20 100 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 lacquer-to-water ratio of 2.5 to 1 (by weight) is suggested for the complete emulsion. "Parlon" of c any viscosity may be used. A typical paint phase for such an emulsion paint is given in Table IX. OS'NM3359 9 STLCOPCB4075006 Table IX. Formulation for Paint Phase of Emulsion Paint Ingredient Parts by Weight "Parlon".......... ............ ..... ......... :............. ............. ............ 28 Aroclor 1254.....*.................. ................... ........................... 14 "Cumar pio"..... :........ ................ ................... ......'!........ . 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 chlorinated rubber compositions plasticized with an Aroclor. These inks are especially useful on soap wrappers and boxes, bottle labels and many other commodities because oftheir alkali resistance. Dsw^36o 10 X STLCOPCB4075007 0 Other Resins and Plasticizers Compatible With Chlorinated Rubber 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 are 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" "Amberol 801, 806P, ST-137, F7" Aroclor 1262, S460 "Aroplaz 920, 930, 935, 940" "Bakelite" XR-3180, XR-4S03, XR-4006, . BR-2963, XJ-9868, BR-1329, BR-3360" "Beckacite 1112" "Beckamine P-138, P-254" "Super-Beckamine 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 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 Santolitc* MPH (sulfonamide-aldehyde resin) . "Stabelite Ester 1, 2, 10" "Stabelite" resin "Super-Beckacite 1001" "Syntex Hi, H3, H12, 17, 213, 22, 28, 29, 32, 36" - "Teglac 15, Z-152" -_,r- - "Velsicol AD6-3" "Vinsol" Table XII. Monsanto Plasticizers Compatible with "Parlon" Aroclor 1242 Aroclor 1254 Aroclor 1260 . Dibutyl phthalate Diethyl phthalate Dimethyl phthalate Santicizcr B-16 (butyl - phthalyl butyl glycolate) Santicizer M-17 (methyl phthalyl ethyl glycolate) Tricresyl phosphate Triphenyl phosphate 0 *Santolite, Santiciier: Monsanto Trademarks. Reg. U.S. Pat Off. 11 DSV\f 323361 STLCOPCB4075008 Toxicity - - . ......_ Animal toxicity studies and 20 years of manufacturing and use experience indicate that Aroclor 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. '' r; `? . Z - - - - - ~---i Repeated 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 Rail Classification - Chlorinated diphenyl (synthetic resin, liquid, NOIBN) Synthetic resin, liquid, NOIBN Snythetic resin, other than liquid, NOIBN .Truck Classification Synthetic resin powder, XSUl Synthetic resin, lumps or solid mass, NOI -- None -- Steel and Fiber (Aroclor 1268, 5460) drums. -- 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 ' --Aroclor 2565 --Aroclor 4065, 4465, 5042, 5060, 5442, 5460 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 ere beyond our control. The Monsanto Chamical 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. 12 DSW 323362 ?) STLCOPCB4075009 VJICtll/SI 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 Cyanamid Company Rohm & Haas Company American Mineral Spirits Co. U. S. Industrial Chemicals Co. Bakelite Company . Reichhold Chemicals, Inc. Reichhold Chemicals, Inc. Reichhold Chemicals, Inc. Reichhold Chemicals, Inc. American Cyanamid Company Carbide & Carbon Cbem. 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" Hercules Powder Company "Neville" Neville Chemical Company "Pentalyn" Hercules Powder Company "Petrex" Hercules Powder Company "Phenac" American Cyanamid Company "Rezyl" American Cyanamid Company "Solvasol" Socony-Mobil Oil Company "Solvesso" Esso Standard Oil . "Stabelite" Ester Hercules Powder Company "Stabelite" Resin Hercules Powder Company "Super-Beckacite" Reichhold Chemicals, Inc. "Syntex" Flintkote Company "Teglac" American Cyanamid Company "Tollac" Neville Chemical Company "Troluoil" Anderson-Pritchard Oil Corp. "Transite" Johns-Manville Sales Corp. "Velsicol" Velsicol Corp. "Vinsol" Hercules Powder Company OS'N STLCOPCB4075010