Document JNgnMdZ6vm7e9aa9r67Egw0DX

AROCLOR resins and plasticizers for chlorinated rubber TECHNICAL BULLETIN N o.PL - 3 11 JANUARY,1958 I /"' I Monsanto I MOMS 078316 ' Thi* bulletin raplecei Monsanto Technical Bulletin No. 0*124 dated May, 1457. HONS 078317 Son* Important applications for protoctivo and dacorativa coating* 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. I MOMS 078318 TABLE OF CONTENTS Pag* Naming of Aroclor Compounds. ........................ -.............. ...................................... 3 Proparties of Chlorinated Rubber '- General........................................ ........................ -.............................................. 4 Physical........................... .................... -............................................................... 4 Chemical Resistance.......................... 4 Electrical..................................... ................................... -.............................. .. 4 Mechanical............................. .... .............................. ........................................... 5 Thermal........................... .................................................................... -..............5 Physical-Chemical..................................................................... 5 Viscosity Types................... 5 Solvent Compatibility................ 6 Formulation and Properties of Chlorinated Rubber Formulation for Aroclor Resins............................................................................6 Formulation for AroclorPlasticizers..................................... 6 Properties of Formulated Films.................... 7 Applications Alkaline-Resistant Coatings...................................................-..........................8 Chemical-Resistant Finishes_________ ___ __________________ _____ -- -- 8 Marine Finishes______________ ________________ ___ ____________________9 Emulsion Points................................................................................................ .. 9 Adhesives................................................................... Paper and Textile Coatings............................................................... -............10 Electrical Coatings............................................................. Printing Inks........................................................ .................................................10 Resins for Chlorinated Rubber.-------------------------------------------------- Monsanto Plasticizers for ChlorinatedRubber................................................................ II Toxicity........................... ............... ................. - - ....................................................... 12 Shipping Information............................... ........................................................................ 12 Trademark Index................................................................................. 10 10 II 13 MCNS 070319 2 .'l AROCLOR resins and plasticizers for chlorinated rubber INTRODUCTION Monsanto produces a series ot 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 adds, alkalies and water), and have good electrical insulating properties. When properly pigmented, these coatings have unusually good weatherability. Chlorinated rubber films plasticized with an Aroclor grip common structural materials in strong adhesive bonds and the 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 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. Aroclor 1248 is a biphenyl with 48 per cent chlorination. Aroclor 5460 is a lerpbenyl with 60 per cent chlorination. Two special mixtures are: Aroclor 4465--a 60:40 mixture (biphenyl to terphenyl) with 65 per cent chlorination. Aroclor IS65--a 75:75 mixture (biphenyl to terphenyi) 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. Thegradual 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. Aroclor: Montanto Trademark. Reg. U S. Pat. Off. 3 HONS 078320 Properties off Chlorinated Rubber "PSrlon" is a mixture of two polymen with an average chlorine content of 67 per cent made by chlorin ating natural rubber. The typical properties of "ParIon" as given by the manufacturer, Hercules Powder Company, Wilmington, Delaware, are listed in Table I. Table 1. Typical Properties of "Parion" General 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 Chemical resistance to: Acids, weak.................................................................................................excellent Adds, 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 (deer unplasticized film*) Specific surface resistance,ohmsXlO1*....................................................2,000 Dielectric strength, volts per mil(ASTM method)................................. 2,300 Dielectric constant at 2SC. 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 Film* used in trdi vrre laid down from toluene aolution. 4 MCNS 078321 Properties, cont'd. .- Mechanical (clear unplasticized film*) 20-cp. type Tensile strength, pounds per square inch, dry............................ 4,270 Tensile strength, pounds per square ineh, wet............................ 4,100 Elongation, per cent, dry................................................................ 3.0 Elongation, per cent, wet................................................................ 3.8 Modulus of elasticity, pounds per square inch............................. 1.4 X10' Hardness, Sward index, per cent of glass..................................... 90 Hot*: Flexibility of *'Prlon" film incrctm with vircority of "Parlon" ured. 1,000-cp.typa 4,850 4,360 5.3 3.4 -- -- Thermal (clear unplesVtcized film*) Burning rate..................................................................................... nonflammable Effect of dry heat on film............................................................stable up to and at 125C. Softening point..................................................................................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.................................................................... . ..Blushes Effect of cold water............................. ..........................................None Moisture absorption (80^f 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 2IC.).............0.2X10* Viscosity Types Viscosity Type 5 cp-....... 10 cp......... 20 cp........ 125 cp....... 1,000 cp....... Table II. *TerlonM 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. In high-solids finishes and as a fortifier for alkyd resin and oleoresinous varnishes and enamels. 20 cp. As a film*former in protectivecoalings 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. Pilmf used in uni were laid down from a toluene rotation. 5 M0NS 078322 Solvent Compatibility Solvents and solvent mixtures suggested for use in preparing formulations with Aroclor and "Parlon" are given in Table 111: Table III. Suggested Solvents for Compositions with Aroclor and "Parlon" MAmsco Sotv," B and E Amyl acetate Butyl acetate Carbon tetrachloride "Cellosolve" Diacetone alcohol Diethyl carbonate Ethyl acetate Ethylene dichloride Hi*Flash naphtha Methyl acetate Xylene Methyl ethyl ketone Methyl isobutyl ketone Methyl salicylate Koto) Octyl, acetate "SovasoF'Nos. 74, 75 "Solvesso 100" "Tollac" Toluene "Union Aromatic Solvent" 3553-10 "Union Solvent No. 30" Formulation! 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 plasticiser types, Aroclor 1242, 1254 and 1260, also show good compatibility. Formulations and properties of films derived from both resin- and plaaticiter-type Aroclor are listed below. Tabla IV. Formulatii Ingredient "Parlon," 20-cp...............................................16 Aroclor 5460.............. .................................... 6 Dibutyl phthalate...........................................-- Tung oil, Thermolyzed, 976........................ -- Xylene or butyl acetate............................... 76 for Aroclor Resin Parts by Weight 16 16 12 12 8 8 12 12 43 5-- 72 71 76 73 12 12 3. 72.. Table V. Formulations Ingredient "Parlon," 20-cp.............................................. 20 Aroclor 1254 or 1260.................................. 4 Xylene.............................................................. 76 Aroclor Ptasticixer Parts by Weight 20 7 73 20 20 70 MCMS 078323 6 Film* cast from these lacquers show improved characteristics due to Aroctor. Some of their advantages are listed below: Adhesion . Unplasticised chlorinated rubber films have very poor adhesion. The lacquer film containing Aroctor 5460 gave good adhesion to aluminum, bare steel, primed steel, galvanized iron and "Transite" surfaces. Othea commercial resins, particularly'oil-modified alkyd resins, gave better adhesion to glass, tin, copper, sealed wood and cellophane. The lacquer films plasticized with Aroctor 1254 or 1260 gave good adhesion to "Transite," cellophane, gal vanised Iron and primed steel surfaces. Some of the other commercial plasticizers tested in similar films pve better adhesion to aluminum, tin, bare steel, copper and sealed wopd surfaces. Though compounds with an Aroctor alone possess pronounced adhesive qualities, better adhesion to all of the surfaces results if mixtures of Aroctor or varied contents are used. Resistance to Aqueous Solutions Chlorinated rubber films with Aroctor 1254 or 1260 (plasticizers) and .tractor 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 Aroctor 5460 In ratios of 5:10 and 10:10 (Aroctor:"Parlon") than with other commercial resins in similar mixtures. Likewise, softer films result from Aroctor 1254 or 1260 in ratios of 2:10 and 5:10 (Aroclor-"Pw\on") than with other commercial plasticizers at these concentrations. From these tests compounds with Aroctor are shown to have strong plasticizing action on chlorinated rubber. Cold-Check Resilience Aroctor 5460 is superior to phenol formaldehyde resins in cold-check resistance imparted to chlorinated rubber films, but not as good as aikyds modified with long oil. Aroctor 1260 used as a plasticizer proved somewhat better than Aroctor 1254. Weather Resistance Pigmented chlorinated rubber finishes containing Aroctor 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 Propartias Plastic films compounded with "Parlon" and containing Aroctor 5460, 1254 and 1260 have shown satisfac tory sanding and polishing characteristics. 7 MGNS 0783ZH Applications AKilint'KttitUnl Coatings ProdttCt 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 paint formulation is given in Table VI. Tabla VI. Paint Formulation for Alkaline Surface (Parts by Weight) Ingredient Formula 1 (katamant (loan) Formulation Formula 2 (Fad. Spac. TT-MI) "Plrlon," 20-cp. lype........... Aroclor 1Z54........................... "Rnyl 869"............................ Aroclor 5460 or "Cumar P10"............... "Beckoso! 31"......................... Tung oil, Thermolyzed, 976. Titanium dioxide.................... Zinc oxide Silica flour Carbon black Xylene..... Hi-Flash naptha..................... Totals......................... 18 10 8 -- -- -- 16 2 3 0.2 42.8 -- 100 18 10 -- 6 -- -- 16 2 -- 0.5 47.5 -- 100 Formula 1 (swimming pooh) 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 ond plasticizers for chemical-resistant paints. Chlorinated rubber formulations with an Aroclor have proved outstanding for acid and alkali resistance. Five formulations re shown In Table VII. Table VII. Formulations for Chemical-Resistant Paints (Parts by Weight) t Ingredient 1 Intatior icMi and alkallai I Eiterlor MO, acids Formulation 2 Eatartor a, alkalies 4 Matrmum rashtanea. acids and akallas 1 Soap rawstant "Parlon," 20-cp. type........... Aroclor 5460........................... "Bakeiite XJ-12895"............ 16 6.4 -- 16 -- 16. -- 6.4 18 -- -- 12 6 -- "Rezyl 807" (solids)................. -- 6.4 --- -- Aroclor 1254........................... 8 4.8 4.8 8 Aroclor 1260.... -.................... -- -- -- 6 Tung oil, Thermolyzed, 976.. -- 4.8 4.8 -- Iron oxide.......................................... 16 16 16 18 Titanium dioxide.................... -- -- -- -- ' Zinc oxide........................................... -- -- -- -- Zylene...................................... 53.6 52 52 39 Hi-Flash naphtha.................. -- -- -- 11 Toluene.................................................. -- -- -- -- Totals......................... 100 100 100 100 -- -- _ 7.7 -- 18 6 28 10.3 12 100 HONS 078325 8 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 bad excellent resistance to acids, alkalis and salt solutions. It also showed good adhesion to glass and other surfaces. Formula S 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. Marina 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 tbeir 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 Feint Ingredient Parts by Weight "Parlon," 20-cp. type............... 20 Aroclor 1254..................................................................... 6 "Reayl S69"............................................................................. 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 lacquer-to-water ratio of 2.5 to 1 (by weight) is suggested for the complete emulsion. "Park>n" of any viscosity may be used. A typical paint phase for such an emulsion paint is given in Table IX. 9 HONS 076326 TabJa IX Formulation for Paint Phasa of Emulsion Paint Infndiinl Parts by Waighf "Partea**................ Arochr 12S4..,,.... "Cutnar P10"....... Xylene................... Hi>Flasb naphtha. Total....... 28 14 n 24 24 100 Adhastvai Chlorinated rubber adhesives with an Arochr 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 Adhetiva fi9rodiont Parti by Weight "Parlon," 125-cp. type.......................................................... 20 Aroclor 1254........................................................................... 6 Aroclor 1260............................................................................ 6 Toluene..................................................................................... 68 Total........................................................................... 100 Papar 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 Ink Printing inks requiring a fast drying time and cheirica! resistance are often based on chlorinated rubber compositions plasticised with an Arochr. These inks are especially useful on soap wrappers and boxes, bottle labels and many other commodities because of their alkali resistance. MGNS 018321 10 Othtr Rnint and FtatHcixn Compatible With Chlorinat'd Rubber The resins and Monsanto plasticizers given in Tables XI and XII are compatible with chlorinated rubber, but none gives the over-alt desired qualities attained by using an Arac/or. 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" Arodor 1262, 5460 MAroplax 920, 930, 935, 940" "Bakellte" XR-31S0, XR-4503, XR-4006, BR-2963, XJ-9868, BR-1329, BR-3360" "Beckaclte 1112" "Beckamlne P-138, P-254" "Super-Beckamlne 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-5I, 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" "Penialyn A, G, M, X" "Petrex 1, 130H" "Phenac 633-M" "Reayl 116, X315, 412, 775, 803, 807, 829, 869, 880, 1103" Rosin Sentolitc* 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" "Velsicol AD6-3" "Vinsol" Table XII. Monsanto Pla ixars Compatible with "Parlon" Aroclor 1242 Arodor 1254 Aroclor 1260 Dibutyl phlhalate Diethyl phthalate Dimethyl phthalate Sautieizcr B-16 (butyl phthatyl butyl glycolate) Sautieizcr M-17 (methyl phthalyl ethyl glycolate) Trlcresvl phosphate Triphenyl phosphate Samiritcr Monunto Trademarks. j. U.S. Pat Off. 11 HONS 078328 Toxicity Animal toxicity studies and 70 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. , 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 Refutations 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, Nul Synthetic resin, lumps or solid mass, NOI -- None -- Steel and Fiber (Aroclor 1268, 5460) drams. -- 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 U. to our host brawledgo. true end accurate, but *11 recommendation! or sefgoitreni ere mod# without guarantee. since the condition! of ue ero beyond our control. The Momenta Chemical Company ditcleimi any liability incurred in connection with the me of thete date or urggettiom. Furthermore, nothing contained herein iheN be construed e* e recommendation to ute any product in conflict with editing patent! covering any materiel or its ate. U HONS 078329 n:tNta-t/w Trademark Indax Trademark "Aerosol OT" "Amberol" HAmsco Sohr" "Aroplaa" "Bakellte" "Beckacite" "Bcckamine" "Beckopol" "Beckosol" "Beetle" Resin "Cellosoive" "Clorafln" "Cumar" "Duraplex" "Esterol" "Fonnvar" "Gelva" "Glyptol" "Hercolyn" Company American Cyanamld Company Rohm it Haas Company American Mineral Spirits Co. U. S. Industrial Chemicals Co. Bakelite Company Reichhold Chemicals, Inc Rekhhold 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. Sonneborn Sons, Inc Shawinigan Resins Corp. Shawinigan Resins Corp. General Electric Company Hercules Powder Company "Lewisor "Neville" "Pentalyn" "PMrex" "Phenac" "ResyT "Solvaaol" "Solvesao" "Stabdite" Ester "Stabelite" Resin "Super-Beckacite" "Syntax" "Teglac" "Tollac" "Troluoil" "Transit*" "VeWcol" "Vinaot" 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 him* n I I I. MONS 078330 13