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AROCLORS * As Used in Chlorinated Rubber
Chemicals Monsanto Technical Bulletin No. P-124
January 1, 1948
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Monsanto Chemical Company, St. Louis 4, Mo.
AROCLORS. chlorinated biphenyl and chlorinated poly-phenyls, are effective plastidzen and resins for chlorinated rubber base lacquers, varnishes and paints. These protective coatings are used where flame resistance, corrosion resistance, chemical resistance, i.e., resistance to adds, alkalies and water, and good electrical insulating properties are required. Some of the important applications for these protective and decorative coatings for wood, metal, brick, stone, concrete and fabric surfaces include: 1. Wood and metal used in the construction of yachts, barges and other marine craft. 2. Structurel steel for bridges, buildings, roofs and power-line structures. 3. Structural materials used at chemical plants, pulp and paper mills, textile mills,
petroleum refineries and gas works where protection against add fumes, alkalies and gas is essential. 4. For the protection of tank cars and other rolling stock and construction machinery against corrosive materials and weathering. 5. To protect equipment used in electroplating and as stop-off lacquers in this industry. 6. Masonry floors and walls. Concrete swimming pools and traffic paints. 7. As cable coatings requiring nonflammability, chemical resistance, water resistance and excellent electrical properties. 8. Coatings for doth to isjpart "waterproofing" qualities as well as chemical and flame resistance.
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AROCLORS AS USED IN CHLORINATED RUBBER
I. INTRODUCTION
Arodors, chlorinated biphenyl and chlorinated poly-phenyls, are used effectively as resins and plasticizers to impart desired qualities to chlorinated rubber, such as Hercules' Parlon.
Parlon is made by chlorinating natural rubber, yielding a mixture of two polymers possessing an average chlorine content of 67 per cent.
II. PROPERTIES OF CHLORINATED RUBBER
The typical properties of Parlon as given by Hercules Powder Company, Wilmington, Delaware, are listed in the following Table I:
General
TABLE I. TYPICAL PROPERTIES OF PARLON
Form as shipped ................. Color of film.......................... Odor...................................... Clarity of film..................... Taste...................................... Moisture, per cent as shipped
White granular powder Water white None Good None
0.5 maximum
Physical
Specific gravity..................................................................................................1.64 Specific volume, as shipped, in cubic inches per pound..........................16.9 Bulking value, gallons per pound................................................................ 0.0735 Index of refraction......................................................................................... 1.554
Electrical (dear unplastidzed film*)
Spedfic surface resistance, ohms x io10.......................................................2,000 Dielectric strength, volts per mil (A.S.T.M. method)..............................2,300 Dielectric constant at 25C. and 1,000 cydes.......................................... 3.1 Power factor at 25C. and 1,000 cydes....................................................... 0.0015 to 0.0030 Power factor at 25C. and 1,000 cydes, after immersion in water for 140
hours and surface wiped dry................................................................ 0.0027
Mechanical (dear unplastidzed 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 elastidty, pounds per square inch..............................1.4 x io5 Hardness, Sward index, per cent of glass...................................... 90
Flexibility of Parlon film increases with viscosity of Parlon used.
1,000-cp. type
4,850 4,360
3-3 3-4
Thermal (clear unplastidzed film*)
Burning rate......................................................................................... nonflammable Effect of dry heat on film ................................................................ stable up to and at i25C. Softening point..................................................................................... decomposes at 135 to 150C.
Physical-Chemical (dear unplastidzed film*)
Sunlight, effect of................................................................................. Discolors and embrittles Aging, effect of..................................................................................... Very slight Water, hot, effect of............................................................................. Blushes Water, cold, effect of........................................................................ None Moisture absorption (80% relative humidity for 24 hours),
percent......................................................................................... . . 0.27 Moisture vapor permeability of 0.003-inch film (grams water/
square centimeter/o.oi centimeter/hour at 21 C.) . . . . 0.2 x io4
* Films used in tests were laid down from a toluene solution.
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General resistance to:
Adds, 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
Different viscosity types of Parlon and suggested uses are given in Table II.
TABLE II. PARLON VISCOSITY TYPES
Viscosity Type
Viscosity Range (in ceptipoises)
5-cp.
IO-Cp. 20-Cp.
125-Cp. 1,000-cp.
5 to 7 8 to 12 16 to 25 no to 190 800 to 2,000
Examples of actual or suggested applications of the several viscosity types are given:
Type
Use Examples
5-CP*
20-cp. 125-cp. 1,000-cp.
In printing inks and as a fortifier for alkyd resin enamels. In high-solids finishes and as a fortifier for alkyd resin and oleoresinous varnishes and
enamels.
As a film-former in protective coatings and as a fortifier in enamels and varnishes. As a film-former in protective coatings, in paper lacquers, adhesives, and textile finishes. As a film-former in adhesives, textile finishes and other finishes where flexibility is
important.
III. SUGGESTED SOLVENTS FOR AROCLOR AND CHLORINATED RUBBER COMPOSITIONS
Solvents and solvent mixtures suggested for use in preparing Arodor and Parlon formulations are given in the following Table III:
TABLE III. SUGGESTED SOLVENTS FOR AROCLOR AND PARLON COMPOSITIONS
SOLVENTS
Amsco Solv, B and E Amyl acetate Butyl acetate Carbon tetrachloride Cellosolve Diacetone alcohol Diethyl carbonate Ethyl acetate Ethylene dichloride Hi-Flash naphtha Methyl acetate
Methyl ethyl ketone
Methyl isobutyl ketone Methyl salicylate Notol Octyl acetate Sovasol Nos. 74, 75 Solvesso 100 Tollac Toluene
Union Aromatic Solvent 3553-10 Union Solvent No, 30 Xylene
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MIXED SOLVENTS
70:30
97:3 83:17 41 : 7: 35 :17 30:70 18 :59 :23 64:36 30 : 30 : 40 40:60
30:70 70:30 85:15
Acetone: hexane Acetone: mineral spirits Benzene: isopentane Cellosolve: ethanol (anhydrous): ethyl acetate : xylene Cellosolve: turpentine Cellosolve: turpentine ; mineral spirits Ethyl acetate: isopentane Ethyl acetate: isopropyl acetate: Troluoil Methyl isobutyl ketone: Troluoil Hi-Flash solvent naphtha: turpentine Methyl acetate: isopentane Shell TS-28 : xylene
IV. AROCLOR AND CHLORINATED RUBBER. PLASTICS FILMS
The resinous Arodors 1262 and 5460 show good miscibility with chlorinated rubber films as laid down from toluene solution containing 20 per cent of the plastics, using 2 :1 and 1:1, Parion : resin, ratios. Similarly, the plasticizer type Arcelor 1242, 1254 and 2260 show good miscibility in chlori nated rubber. The properties of films derived from the following formulations containing either Parion and resinous Arodors 1262 or 5460, or Parion and the plasticizer type Aroclors 1242,1254 or 1260 were studied.
RESINOUS TYPE AROCLOR FOR PARLON PLASTICS
Ingredients
Parts by wdght
Parion, 20-cp........................................... .... 16 16 16 12
Arodor 5460........................................... .... 8 8 8 12
Dibutyl phthalate..................................
4
Tung oil, Thermolyzed, 976 ... .
5
Xylene or butyl acetate..................... .... 76 72 71 76
12 12
3
73
12 12
3-75 72-25
PLASTICIZER TYPE AROCLORS FOR PARLON PLASTICS
Ingredients
Parts by wdght
Parion, 20-cp...........................................
20 20
Arodor 1254 or 1260......................... .... 4
7 20
Xylene................................................... .... 76 73 70
Examination of the films cast from these lacquers revealed the following characteristics imparted by the Arodors:
Adhesion'. -- Unplastidzed chlorinated rubber films have very poor adhesive qualities. The lacquer film containing Aroclor 5460 gave good adhesion to aluminum, bare steel, primed steel, galvanized iron and Transite surfaces. Other commercially available resins, particularly oil modified alkyd resins, tested in similar films gave better adhesion than Aroclor 5460 to such surfaces as glass, tin, copper, sealed wood and cellophane. The lacquer films plasticized with Arodors 1254 or 1260 gave good adhesion to Transite, cello phane, galvanized iron and primed steel surfaces. Some of the other commercially available
plasticizers tested in similar films gave better adhesion than the Aroclors to aluminum, tin, bare steel, copper and sealed wood surfaces. Arodors, alone, possess pronounced adhesive qualities. Doubtless, where the objective is to produce adhesives, by varying the Arodor content or by using a mixture of Arodors in the chlorinated rubber lacquers, much better adhesion to all of the surfaces would be accomplished than was the case with the type of plastics films studied. Resistance to Aqueous Solutions:-- Aroclors 1254 or 1260 used as plastidzers and Arodor 5460 used as a resin in chlorinated rubber produced plastics films possessing satisfactory resistance
to 10 per rant hydrochloric add, 5 per cent sodium hydroxide, 5 per cent sodium chloride solutions and to water spot tests.
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Film HardnessUsing Arocloi 5460 in ratios of 5 : xo and 10 :10, Arodor: Parlon, decidedly softer films were produced than when other commercial resins were similarly used. Likewise, Aroclors 1254 or 1260 used in ratios of 2:10 and 5 :10, Arodor: Parlon, gave softer films than obtained from other commercial plasticizers, used at these concentrations. This indicates the strong plasticizing action of these Arodors on chlorinated rubber.
Cold-Check Resistance:--Regarding cold-check resistant qualities imparted to chlorinated rubber films, Arodor 5460 is somewhat superior to Bakelite type resins, but not as good as long-oil modified alkyds. Arodor 1260 used as a plastidzer rates, in terms of cold-check resist ance, somewhat better than Arodor 1254 and nearly as good as the best of the other plasticizers studied for this property.
Miscellaneous Properties:-- Parlon plastics films containing Arodors 5460, 1254 or 1260 have entirely satisfactory sanding and polishing characteristics.
Weatherability:-- Pigmented chlorinated rubber finishes containing Arodors have consistently shown good outdoor weatherability. However, similar unpigmented finishes, regardless of the plastidzer or resin used and also in the absence of these additives, have been found to give poor outdoor weathering. Relatively poor resistance to ultraviolet light is a weakness of chlori nated rubber.
Most pigments, with the exception of ultra-marine blue are usable with Parlon finishes and are recommended when the coating is to be subjected to outdoor weathering or exposed to ultra violet light. However, there is considerable variation regarding the protection offered by different pigments. Inspection of Parlon-fortified alkyd enamels showed the weatherability varied from 63 months for the enamel pigmented with chrome green to 4 months for enamel pigmented with a titanium dioxide-iron blue combination.
V. USES FOR AROCLORS IN CHLORINATED RUBBER COATINGS
A. Finishes for Alkaline Surfaces:
Arodors, as well as chlorinated rubber, are highly resistant against alkalies and moisture. Because of these properties paints based on Arodor and chlorinated rubber combinations are used in large quantity for application to concrete floors, walls, swimming pools, etc Examples of this type of paint are given in Table IV.
TABLE IV. AROCLOR PLASTICIZER IN CHLORINATED RUBBER PAINTS
FOR ALKALINE SURFACES
(Examples of starting formulas)
Materials
Formula i for basement floors
Formula 2 to meet Fed. Spec. TT-P-qi
(Parts by weight)
Formula 3 for swimming pools
Parlon, 20-cp. type . . . . .....................
18
18
14.6
Arodor 1254.............................
10 44
Rezyl 869.............................. ......................
8
Arodor 5460 or Cumar Pro
6
Beckosol 31 .......................... Tung oil, Thermolyzed, 976 Titanium dioxide................. Zinc oxide.............................. Silica flour.............................. Carbon black......................... Xylene...................................... Hi-Flash naphtha.................
Totals.....................
...................... ......................
16 3
16 2
0-5 47-5
100
2.9 4-4 19.7 65
47-5 IOO
B. Acids and Alkali-Rssistant Finishes:
Particular care must be exercised in the choice of resins and plasticizers for use in chemical resistant paints. For this purpose, Arodors are outstanding and are being used successfully in the add and alkali-resistant chlorinated rubber formulations given in Table V.
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TABLE V. AROCLOR PLASTICIZERS AND RESINS FOR CHLORINATED
RUBBER, ACID AND ALKALI-RESISTANT FINISHES (Example* for starting formulations)
Materials
1 For interior use against
acids and alkalies
Parlon, 20-cp. type................. Arodor 5460.............................. Bakelite XJ-12895..................... Rezyl 807 (solids)..................... Arodor 1254.............................. Arodor 1260.............................. Tung oil, Thermolyzed, 976 . Iron oxide.................................. Titanium dioxide..................... Zinc oxide.................................. Zylene.......................................... Hi-Flash naphtha..................... Toluene......................................
. .
16 -4 8
53-6
2 For exterior use against
adds
,, 4. For exterior For maximum
use against resistance to
alkalies
adds and
alkalies
(Pans by weight)
16 16 18
6.4 6.4 4.8 4.8 8
6
4-8 4.8 l6 16 18
52 52 39 11
For use against
soap solutions
12 6
7-7
18 6 28 10.3 12
Totals......................... . 100 100 100 100 100
The paints given in Table V were applied to metal bars or panels and tested. Formula i, an interior paint, showed good resistance to a io per cent hydrochloric add solution and to a 5 per cent sodium hydroxide solution. The add resistant paint described under the heading of Formula 2 has shown excellent outdoor protection to metal surfaces on add manufacturing plants. Similarly, paints based on Formula 3 have given good outdoor performance on alkali producing plants. Paint based on Formula 4 was found to have excellent resistance to adds, alkalies and other corrosive materials such as salt solutions. Moreover, this paint showed good adhesion to various surfaces induding glass. Paint based on Formula $ is indicated to have good resistance against warm aqueous solutions containing soap. It should be pointed out that Arodor and chlorinated rubber finishes are not recommended for continuous exposure at temperatures above I40F.
C. Marine Finishes:
Arodor plastidzed chlorinated rubber coatings possess good resistance to salt water and their hard finish deters algae and marine growths from adhering to them. These qualities and good chemical resistance indicates the usefulness of these paints to protea wood and metal used in making boats, barges and other marine equipment. A suggested formula for a marine paint is given in Table VI.
TABLE VI. AROCLOR PLASTICIZER FOR A CHLORINATED RUBBER
MARINE WHITE PAINT
(Starting formulation)
Materials
Pans by weight
Parlon, 20-cp. type................................................... Arodor 1254................................................................ Rezyl 869.................................................................... Titanium dioxide........................................................ Xylene........................................................................ Hi-Flash naphtha.......................................................
. 20 .6 .6 . 25
23
. 20
Total
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D. Emulsion Paints:
Aroclor 1254 is used in chlorinated rubber emulsion paints recommended when chemical resistance is required on porous surfaces. Hercules Powder Company report that the preferred water phases for such paints are either a 1 per cent solution of Aerosol OT in distilled water or a 4 per cent solu tion of sodium oleate in distilled water. For the complete emulsion, a ratio by weight of lacquer phase to water phase of 2.5 to 1 is suggested. Parlon of any desired viscosity pray be used. A typical paint phase for the Aroclor-Parlon emulsion paint contains the following ingredients:
PAINT PHASE FOR THE EMULSION
Ingredients
Parlon................. Aroclor 1254 . , Cumar Pio . . . Xylene .... Hi-Flash naphtha
Total .
Parts by weight , 28
14 10
_21 100
E. Adhesives:
Aroclor and chlorinated rubber adhesives are resistant to chemicals and were developed originally for adhering labels to add bottles. These adhesives are also of unusual interest because of their good fire resistant qualities. A typical formulation contains the following ingredients:
AROCLOR PLASTICIZERS FOR CHLORINATED RUBBER ADHESIVES
Ingredients
Parlon, 125-cp. type Aroclor 1254 . . . Aroclor 1260 . . . Toluene.................
Total . .
Parts by weight
. 20
.6
.6
68 . 100
F. Paper and Textile Coatings:
Aroclor and chlorinated rubber coatings are worthy of consideration for specific end uses in the paper and textile coatings fields. In general, however, the use of this type of coating in these fields may be restricted especially where freedom from odor and taste are required. Unpigmented Aroclor and chlorinated rubber finishes would seem suitable for certain fabrics used indoors, but not where they are exposed to high temperatures and direct sunlight.
0. Coatings for Electrical Apparatus:
Because of their desirable electrical properties, compositions containing Aroclors and chlorinated rubber are very useful to insulate and protect electrical wire and apparatus from moisture. When fortified with selected fungistats and waxes, coatings of this type are used to "tropicalize" or protect electronic equipment against both moisture and fungi. Moreover, the fire resistant qualities of these plastics are highly desirable for use in the electrical field.
H. Inks:
Aroclor plasticized chlorinated rubber compositions are very useful for printing inks where faster drying tune and increased chemical resistance are desired. The alkali-resistant properties of such plastics suggest their use in the printing of soap wrappers and soap boxes, bottle labels and other commodities where the ink must be resistant to alkalies.
VI. RESINS AND PLASTICIZERS, OTHER THAN AROCLOR, MISCIBLE IN CHLORINATED RUBBER
The resins and plasticizers given in the following Table VII are miscible in chlorinated rubber. This was determined by the examination of films laid down from 2 : i.and x : 1, Parlon : resin or plasticizer ratios at 20 per cent concentration in toluene.
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TABLE VII. RESINS AND PLASTICIZERS MISCIBLE IN PARLON
RESINS
Amberol 801, 806P, ST-137, F7 Aroclor 1262, 5460 Aroplaz 920,930, 935, 940 Bakelite XR-3180, ^-4503, XR-4006,
BR-2963, XJ-9868, BR-1329, BR-3360 Beckadte 1112 Beckamine P-138, P-254 Super-Beckamine 3501 Beckopol 1400 Beckosol 1 (solid), i8( 31, 34,40, 1329 Beede Resin 227-8 Clotafin 70 Copal Cumar Pio Dammar
Duraplex C-45-LV, C-48, C-49, C-50-LV, C-51, C-62, D-61, D-62, E-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 MHP Staybelite Ester j, 2,10 Staybelite resin Super-Beckadte 1001 Syntex Hi, H3, H12,17, 213, 22, 28, 29, 32, 36
Teglac 15, Z-152
Velsicol AD6-3 Vinsol
Amylchloro naphthalene Amyl oleate Amyl stearate Arodor 1242 Aroclor 1254 Aroclor 1260 Butyl myristate Butyl stearate Camphor Castor oil, raw Castor oil, dehydrated Castor oil fatty add esters Ccllosolve phthalate Coconut fatty add esters Diamyl naphthalene Diamyl phthalate Dibutyl phthalate Dibutyl sebacate Diethyl phthalate Dimethyl phthalate Fish oil
Hercolyn Linseed oil
PLASTICIZERS
Methyl cellosolve oleate Monoamyl naphthalene Naftolen Neville heavy oil No. 2 Neviilite oil Oiddca oil Palm fatty add esters Perilla oil Polyamyl naphthalene Resinous Products C-24 Santidzer B-16 Santidzer M-17 Sextol phthalate Sextol stearate Soya bean fatty add esters Soya bean oil Thermoil A Tributyl phosphate Tricresyl phosphate Triethyl dtrate Triphenyl phosphate Tung oil, Thermolyzed, 976
The strong points and limitations of the resins and plasticizers given in Table VII relative to the properties they impart to chlorinated rubber are known. None give the important over-all desired qualities attained by the use of Arodors. If occasion arises to consider the use of these materials in spedfic applications for chlorinated rubber, then more detailed information about them will be given.
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VII. GENERAL
Prior to Word War II Arodors, used in substantial amount with chlorinated rubber, made rapid growth in the applications given in this report. During the war, scarcity of natural rubber curtailed these developments but since the war industry has been quick to resume the use of Aroclor plas ticized chlorinated rubber compositions.
Their principal field of application is as lacquers, varnishes and paints where flame resistance, cor rosion resistance, chemical resistance, i.e., resistance to adds, alkalies and water, and good electrical insulating properties are required.
When properly pigmented these paints or coatings have good weatherability. Although the adhesion of unplasticized chlorinated rubber films to common structural materials is poor, when plasticized with Aroclon strong adhesive brads are obtained. Arodon improve the flexibility and life of chlori nated rubber plastics coatings.
The formulations of Aroclon and chlorinated rubber along with their suggested uses, as given in this report, are in line with good commercial practice. Much of the data given was obtained from other Anns, particularly Hercules Powder Company, Wilmington, Delaware. The information given is to serve as a guide or souring point in the development of formulations to expand taking advantage of the outstanding qualities of Arodors as resins and plasriazers for chlorinated rubber.
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For furthor information about AROCLORS, write, wire or call the nearest Monsanto office.
MONSANTO CHEMICAL COMPANY
ST. LOUIS
BIRMINGHAM . BOSTON CHARLOTTE CHICAGO CINCINNATI CLEVELAND DETROIT LOS ANGELES NEW YORK PHILADELPHIA PORTLAND (Ort.) . SAN FRANCISCO
MONSANTO (CANADA) LTD. Montreal
Representative! in the Principal Cities of the World.
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