Document mpe9MYK5e0g0brdVBZwrvqknZ
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MONSANTO TECHNICAL BULLETIN No^^124_______
' --4 October 28, 1947
Monsanto Chemical Company
Saint Louis, Missouri
New York-Chicago-Boston-Birmingham-Charlotte-Cincinnati-PhlladelphlaDetrolt-Los Angeles-San Francisco-Montreal
I. INTRODUCTION
The Aroclors*, 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 percent.
II. PROPERTIES OF CHLORINATED RUBBER
The typical properties of Parlon as given by Hercules Powder Com pany, Vilmington, Delaware are listed in the following Table I:
TABLE I. TYPICAL PROPERTIES OF PARLON
General Form as shipped Color of film Odor Clarity of film Taste Moisture, percent as shipped
White granular powder Water white None Good None
0.5 maximum
Physical Specific gravity Specific volume, as shipped, in cubic inches per pound Bulking value, gallons per pound
Index of refraction
1.64
16.9
0.0735 1.554
* Registered in U. S. Patent Office.
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Electrical (clear unplasticized film*)
Specific surface resistance,
ohms x 1CT10
-
Dielectric strength, volts per
mil (A.S.T.M. method)
Dielectric constant at 25C.
and 1,000 cycles
Pover factor at 25C. and
1,000 cycles
Pover factor at 25C. and
1,000 cycles, after immersion
in vater for 140 hours and
surface wiped dry
2,000 2,300 3-1 0.0015 to 0.0030
0.0027
Mechanical (clear unplasticized film*) 20-cp. type
1,000-cp. type
Tensile strength, pounds per square inch, dry
Tensile strength, pounds per square inch, vet
Elongation, percent, dry Elongation, percent, vet Modulus of elasticity, pounds
per square inch
Hardness, Sward index, percent
of glass
4,270 4,100 3.8 1.4 x 105 90
4,850
4,360 3-3 3-4
Flexibility of Parlon film increases with viscosity of Parlon used.
Thermal (clear unplasticized film*)
Burning rate Effect of dry heat on film Softening point
nonflammable stable up to and at 125C.
decomposes at 135 to 150C.
Physical-Chemical (clear unplasticized film*)
Sunlight, effect of Aging, effect of Vater, hot, effect of Water, cold, effect of . Moisture absorption (80# relative
humidity for 24 hours), percent
Discolors and embrittles Very slight Blushes None
0.27
0222137
Films used in tests were laid down from a toluene solution.
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Moisture vapor permeability of
0.003-inch film (grams water/
square centimeter/0.01 centimeter/
hour at 21C.)
,
serai resistance to:
Acids, weak Acids, strong Alkalies, weak Alkalies, strong
Salt spray Alcohols Ketones Esters Hydrocarbons, aromatic Hydrocarbons, aliphatic
Oils, mineral Oils, animal Oils, vegetable
, 0.2 x 10-
excellent excellent excellent excellent good excellent soluble soluble soluble good good poor poor
Different viscosity types of Parlon and suggested uses are given in Table II.
TABLE II. Viscosity Type
PARLON VISCOSITY TYPES
Viscosity Range (in centipolses)
5-cp. 10-cp. 20-cp.
125-cp.
1,000-cp.
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:
Type
Use Examples
5-cp.
In printing inks and as a
fortifier for alkyd resin
enamels.
o 10-cp.
In high-solids finishes and as a fortifier for alkyd resin and oleoresinous varnishes and
enamels.
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20-cp. 125-cp. 1,000-cp.
As a film-former in protective coatings
and as a fortifier in enamels and var
nishes.
'
As a'film-former in protective coatings,
in paper lacquers, adhesives, and tex
tile 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 Aroclor and Parlon formulations are given in the following Table III:
TABLE III. SUGGESTED SOLVENTS FOR AROCLOR ---------------Aim 'mmT~UoHPoSITI5HB
Solvents
Amsco Solv, B and E Amyl acetate Butyl acetate Carbon tetrachloride Cellosolve Dlacetone alcohol Diethyl carbonate Ethyl acetate Ethylene dichloride Hi-Flash naphtha Methyl acetate Methyl ethyl ketone
Methyl lsobutyl ketone Methyl salicylate
Notol Octyl acetate
Sovasol Nos. 74, 75
Solvesso 100 Tollac Toluene
Union Aromatic Solvent
3553-10 Union Solvent No. 30 Xylene
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 65:15
acetone:hexane
acetone:mlneral spirits
'
benzene:isopentane .
Cellosolve:ethanol (anhydrous):
ethyl acetate:xylene
Cellosolve:turpentine
Cellosolve: turpentine .`mineral spirits
ethyl acetate:lsopentane
ethyl acetate:Isopropyl
acetate:Troluoll
methyl lsobutyl ketone .`Troluoll
Hi-Flash solvent naphtha:turpentine
Methyl acetate:isopentane
Shell TS-2S:xylene
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IV. AROCLOR AND CHLORINATED RUBBER, PLASTICS FILMS
The resinous Aroclors 1262 and 5460 show good miscibility with chlorinated rubber films as laid down from toluene solution con taining 20 percent of the plastics, using 2:1 and 1:1, Parlon: resin, ratios. Similarly, the plasticizer type Aroclor 1242, 1254 and 1260 show good miscibility in chlorinated rubber.
The properties of films derived from the following formulations containing either Parlon and resinous Aroclors 1262 or 5460, or Parlon and the plasticizer type Aroclors 1242, 1254 or 1260 were studied.
RESINOUS TYPE AROCLOR FOR PARLON PLASTICS
Ingredients__________________ _________;________ Parts by weight
Parlon, 20-cp. Aroclor 5460 Dlbutyl phthalate Tung oil, Thermolyzed, 976 Xylene or butyl acetate
16 8
76
16 8 4
72
16 12 12 8 12 12
3 5 71 76 73
12 12
3.75 72.25
PLASTICIZER TYPE AROCLORS FOR PARLON PLASTICS
Ingredients___________________________________Parts by weight
Parlon, 20-cp. Aroclor 1254 or 1260 Xylene
20 4
76
20 7
73
20 20 70
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Fxamination of the films cast from these lacquers revealed the fol lowing characteristics imparted by the Aroclors.'
Adhesion; - Unplasticized 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, parti cularly oil modified alkyd resins, tested in similar films gave better adhesion than Aroclor 5460 to such surfaces as glass, tin, copper, sealed wood and cello phane .
The lacquer films plasticized with Aroclors 1254 or 1260 gave good adhesion to Transite, cellophane, gal vanized iron and primed steel surfaces. Some of the other commercially available plasticizers tested in similar films gave better adhesion than the Arodlors to aluminum, tin, bare steel, copper and sealed wood surfaces.
Aroclors, alone, possess pronounced adhesive qualities, Doubtless, where the objective is to produce adhesives, by varying the Aroclor content or by Using a mixture of Aroclors in the chlorinated rubber lacquers, much better adhesion to all of the surfaces would be accom plished than was the case with the type of plastics films studied.
Beslstance to Aqueous Solutions; * Aroclors 1254 or 1260 used as plasticizers and Aroclor 5460 used as a resin in chlorinated rubber produced plastics films possessing satisfactory resistance to 10 percent hydrochloric acid, 5 percent sodium hydroxide, 5 percent sodium chloride solutions and to water spot tests.
Film Hardness: - Using Aroclor 5460 in ratios of 5:10' and 10:10, Aroclor: Parlon, decidedly softer films were produced than when other commercial resins were simi larly used. Likewise, Aroclors 1254 or 1260 used in ratlOB of 2:10 and 5:10, Aroclor: Parlon, gave softer films than obtained from other commercial plasticizers, used at these concentrations. This indicates the strong plasticizing action of these Aroclors on chlorinated rubber.
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Cold-Check Resistance: - Regarding cold-check resistant qualities Imparted to chlorinated rubber films, Aroclor 5460 is somewhat superior to Bakellte type resins, but not as good as long-oil modified alkyds. Aroclor 1260 used as a plasticizer rates, in terms of cold-check re sistance, somewhat better than Aroclor 1254 and nearly as good as the best of the other plasticizers studied for this property.
Miscellaneous Properties: - Parlon plastics films con't'a'ln'ing" Aroclors 5460, 1254 or 1260 have entirely sat isfactory sanding and polishing characteristics.
Weatherablllty: - Pigmented chlorinated rubber finishes containing Aroclors have consistently shown good outdoor weatherablllty. However, similar unpigmented finishes, regardless of the plasticizer 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 chlorinated 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 ultraviolet light. However, there is consi derable variation regarding the protection offered by different pigments. Inspection of Parlon-fortified alkyd enamels showed the weatherablllty 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: '
'
Aroclors, as well as chlorinated rubber, are highly resistant
against alkalies and moisture. Because of these properties paints based on Aroclor 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 TV.
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TABLE IV. AROCLOR PLASTICIZER IN CHLORINATED RUBBER
Pa'IKTS For ALKALINE SURFACES
"
(Examples of starting formulas)
Parts by weight
Formula 1 Formula 2 to
Formula 3
for base- meet Fed. Specif, for swlm-
Materlals________________ment floors TT-P-91_____________ mlng pools
Parlon, 20-cp. type Aroclor 1254
Rezyl 869 Aroclor 5^60 or Cumar P10
Beckosol 31 Tung oil, Thermolyzed, 976
18 10
8
18 10
6
14.6 4.4
4.4
Titanium dioxide Zinc oxide Silica flour Carbon black
Xylene HI-Flash naphtha
16 2 3 0.2
42.8
16 2
0.5
47.5
19.7 6.5
47.5
Totals
100 100
100
B. Acids and Alkali-Resistant Finishes;
Particular care must be exercised In the choice of resins end plasticizers for use In chemical resistant paints. For this purpose, Aroclors are outstanding and are being used successfully In the acid and alkali-resistant chlorinated rubber formulations given in Table V.
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TfiRT.-R v. aroclor plasticizers and resins for chlorinated rubber, --------------------------ACID aND"aLK/XiI-1TE5I5TaN'1i FINISHES
(Examples for starting formulations)
Materials
1 23 For lnte- For exte - For exte rlor use rlor use rlor use against agains t against acids and acids alkalies
alkalies
4 For maximum resistance to acids and alkalies
5 For use against soap solu-
tlons
(Parts by weight)
Parlon, 20-cp. type
16
Aroclor 5460
6.4
Bakelite XJ-I3895
Rezyl 807 (solids)
16 6.4
16 6.4
18
12 6
Aroclor 1254 Aroclor 1260 Tung oil, Ther-
molyzed, 976
Iron Titanium dioxide Zinc oxide
8 16
4.8
' 4.8 16
4.8
4.8 16
8 6
18
7.7
18 6
Xylene
Hi-Flash naphtha Toluene
53-6
52
52
39 11
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 1, an interior paint, showed good resistance to a 10 percent hydrochloric acid solution and to a 5 percent sodium hydroxide solution. The acid resistant paint described under the heading of Formula 2 has shown excellent outdoor protection to metal surfaces on
0222M*
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acid 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 resistant to acids, alkalies and other corrosive materials such as salt solutions. Moreover, this paint showed good adhesion to various surfaces in cluding glass. Paint based on Formula 3 is Indicated to have good resistance against warm aqueous solutions containing soap.
It should be pointed out that Aroclor and chlorinated rubber finishes are not recommended for continuous exposure at temperatures above l40F.
C. Marine Finishes;
Aroclor plasticized 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 use fulness of these paints to protect wood and metal used in making boats, barges and other marine equipment. A sug gested formula for a marine paint is given in Table VI.
TABLE VI. AROCLOR PLASTICIZER FOR A CHLORINATED RUBBER MARINE AffilTSTFAlfT
(Starting formulation)
Materials
Parlon, 20-cp. type Aroclor 125A Rezyl 869 Titanium dioxide Xylene Hi-Flash Naphtha
Total
Parts by weight
20
6 6
25 23 20
100
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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 percent solution of Aerosol OT in distilled water or a 4 percent solution 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 may be used. A typical paint phase for the Aroclor-Parlon emulsion paint contains the following ingredients:
Paint Phase for the Emulsion
Ingredients
Parts by weight
Parlon Aroclor 1254
Cumar P10 Xylene Hi-Flash naphtha
28 14
10 24 24
Total
100
E. Adhesives:
Aroclor and chlorinated rubber adhesives are resistant to
chemicals and were developed originally for adhering labels
to acid 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
Parts by weight
Parlon, 125-cp. type
Aroclor 1254 Aroclor 1260 Toluene
20
6 6 68
Total
100
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P. 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 vhere 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.
G. Coatings for Electrical Apparatus:
Because of their desirable electrical properties, composi tions 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 time and increased chemical resistance are desired. The alkaliresistant 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 end plasticizers given in the following Table VII are miscible in chlorinated rubber. This was determined by the ex
amination of films laid down from 2:1 and 1:1, Parlon: resin or plasticizer ratios at 20 percent concentration in toluene.
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TABLE VII. RESINS AMD PLASTICIZERS MISCIBLE IN PARLON
..
Resins
Amberol 801,8o6P,ST-137.F7 Aroclor 1262,5460
Aroplaz 920,930,935,940
,,
Bakellte XR-3l80,XR-4503,XR-4006,BR-2963,XJ-9868,
BR-1329,BR-3360 Beokacite 1112
Beckamine P-138, P-254 Super-Beekamlne 3501
Beckopol 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-6l,
D-62,E-71,E-71-A,E-73 East India gum
Ester gum Ethyl Methacrylate
Esterol 750 Formvar
Gelva 2.3 Glyptal 1247,2430,2454,2458,2464,2466,2500
Levisol 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
Santolite MHP Staybelite Ester 1,2,10 Staybelite resin
Super-Beckaclte 1001
Syntex HI,H3,H12,17,213,22,28,29,32,36 Teglac 15,2-152
Velsicol AD6-3 Vinsol
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Plasticizers
Amylchloro naphthalene
Amyl oleate
Amyl stearate
'
Aroclor 1242
Aroclor 1254
Aroclor 1260
Butyl myristate
Butyl stearate
Camphor
Castor oil, raw
Castor oil, dehydrated
Castor oil fatty acid esters
Cellosolve phthalate
Coconut fatty acid esters
Diamyl naphthalene
.
Diamyl phthalate
Dibutyl phthalate
Dibutyl sebacate
Diethyl phthalate
Dimethyl phthalate
Fish oil
Hercolyn
Linseed oil
Methyl Cellosolve oleate Monoamyl naphthalene
Naftolen Neville Heavy Oil No. 2 Nevillite oil
Oticica oil Palm fatty acid esters
Perilla oil Polyamyl naphthalene Resinous Products C-24
Santicizer B-l6 Santiclzer M-17 Sextol phthalate Sextol stearate Soya bean fatty acid esters Soya bean oil
Thermoil A Tributyl phosphate Tricresyl phosphate Triethyl citrate 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 Aroclors. If occasion arises to consider the use of these materials in specific appli
cations for chlorinated rubber, then more detailed information about them will be given.
VII. GENERAL
Prior to World War II Aroclors, 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 plasticized chlorinated rubber composi tions.
Their principal field of application is as lacquers, varnishes and paints where flame resistance, corrosion resistance, chemical resistance, i. e., resistance to acids, alkalies and water, and good electrical insulating properties are required.
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Vhen 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 Aroclors strong adhesive bonds are obtained. Aroclors improve the flexibility and life of chlorinated rubber plastics coatings.
The formulations of Aroclors 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 firms, particularly Hercules Powder Company, Wilmington, Delaware. The information given is to serve as a guide or starting point in the development of formulations to expand taking advantage of the outstanding qualities of Aroclors as resins and plasticizers for chlorinated rubber.
*****#***
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 are beyond our con trol. Monsanto Chemical 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.
rh/PCB
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