Document RpVpaVaKdan7m5VYONgvovBJV
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Monsanto
Chemicals "Plastics
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AROCLOR
S'
2(5.^
As Used in Chlorinated Rubber
Technical Bulletin I
o-uH
Ar-'i > lf*7
January 1, 1948--
Monsanto Chemical Company; ft. Louis / MoP
. *-
AROCLOR!, chlorinated biphenyl and Haiaii poly^phenyls, are effective plastidzen and resins for chlorinated rubber base lacquers, varnishes and paints.
These protective coatings are used
flame resistance, corrosion resistance, chemical
rcsistancAHHHrtHMM(atids, alkalies and water)?and good electrical insulating
properties aaofM.
Some of the important applications for these protective and decorative coatings for
wood, metal, brick, stone, concrete and fabric surfaces include:
'-
'Wood and metal used iitfflHHHMBiMNf yachts, barges and other marine craft.
Stiucturel steel for bridges, buildings, roofs and power-line structures.
Structural materials
at chemical plants^pulp and paper mills, textile mills,
petroleum refineries and gas works
^protection against add fumes, alkalies
andg^MBL
A
^MflfcosjBMaMMflaiik cars and other rolling stock and construction machinery against corrosive materials and weathering.
Equipment used in electroplating and as stop-off lacquers in this industry.
Masonry floors and walls. Concrete swimming pools and traffic paints.
(able coatings requiring nonflammability, chemical resistance, water resistance and excellent electrical properties.
Coatings for doth to impart "waterproofing" qualities as well as chemical and flame resistance.
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AROCliOR^ as used in chlorinated rubber
I. INTRODUCTION
.
Aroclors, chlorinated biphenyl and chlorinated poly-phenyls, are used effectively as resins and plasticizers to impart desired qualities to chlorinated rubber, such as HercuIes'(Parton.'(.
Parlon isjnade by chlorinating natural rubbefe^daMi^a mixture of two polymers aVexagecSorine content of 67 percenj,
% an
------- -- ---------- -------- II. PROPERTIES OF CHLORINATED RUBBER The typical properties of^arlon given by Hercules Powder Company, Wilmington, Delaware,
are listed in ilm fiillirulni, Table I:
TABLE I. TYPICAL PROPERTIES OF PARLON
General
Form as shipped ................. Color of film.........................
White granular powder Water white
Odor...................................... Clarity of film..................... Taste......................................
None Good 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
Electrical (clear unplasticized film*)
Specific surface resistance, ohms x 1010...................................................... 2,000
Dielectric strength, volts per mil (A.S.T.M. method)..............................2,300
Dielectric constant at 25C. and 1,000 cycles
..............................3.1
Power factor at 25C. and 1,000 cycles.......................................................0.0015 10 0.0030
Power factor at 25C. and 1,000 cycles, after immersion in water for 140
hours and surface wiped dry............................................................... 0.0027
Mechanical (clear unplasticized 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 elasticity, pounds per square inch..............................1.4 x io6 Hardness, Sward index, per cent of glass...................................... 90
Flexibility of Parlon film increases with viscosity of Parlon used.
1,000-cp. type 4*850
33 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 I50C.
Physical-Chemical (clear unplastidzed film*)
t
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),
per cent................................................................................................. 0.27 Moisture vapor permeability of 0.003-inch film (grams water/
square centimeter/0.01 centimeter/hour at 2rC.) . . . . 0.2 x 10*
* Films used in tests were laid down from 1 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 OUs, mineral......................... ...............................................................good Oils, animal.............................................. ,........................................ poor Oils, vegetable .....................................................................................poor Different viscosity types ofVarlon^and suggested uses are given 'TnTable-fl.
'TM
TABLE II. Viscosity Type
PARLON VISCOSITY TYPES
Viscosity Range (in centipoises)
5"CP................................................................................................. 10-cp.................................................................................................
5 to 7 8 to 12
20-cp...................................................................................................... 16 to 25
125-cp.................................................................................................... no to 190
1,000-cp.................................................................................................... 800 to 2,000
Examples of actual or suggested applications of the several viscosity types are givent>n-^tO
la* 5-cp.
10-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
enamds. 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 yid other finishes wfrye flexibility^
/ $ / L 1 Ty
Solvents and solvent mixtures suggested for use in preparingAradp^n^ ^arlon^ormuianons^ffe^
given in
Table III:
>
TABLE III. Sl)oQESttfl> SOLVENTS FOR AROCLOR ANDPARLONj^OMPOSITIONS tuiiU \
1 111
SOLVENTS---------------------------------- J
'
^Amsco SolvpB and E^^41 .
&:') Methyl isobutyl ketone
Amyl acetate
,
Methyl salicylate
Butyl acetate
t^Notol -- ^,
Carbon tetrachloride h Cellosolve,,
v
Octyl acetate \ "Sovasol'Nos. 74, 75
-\U*Ul QJL to \
Diacetone alcohol
* ^Solvesso 100''
&UZ)
' *
Diethyl carbonate Ethyl acetate
K^Tollac " / Toluene c
cjq_\
(. Ethylene dichloride
.
.
, . *lJnion Aromatic Solvent 3553-10
t/rHi-Flash"naphtha (Ce.yiJnion Solvent No. 30
Methyl acetate
' Xylene
Methyl ethyl ketone
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70:30 97:3
Acetone: hexane Acetone : mineral spirits
83 :17
Benzene: isopentane
41:7:35 :17 ,teUosolve*: ethanol (anhydrous); ethyl acetate: xylene
30:70 18 :59:23
"Cellosolve/: turpentine '^Cellosolve': turpentine i mineral spirits
64:36 30:30:40
Ethyl acetate ^isopentane
a * j * +
Ethyl acetate : isopropyl acetate iTroliioilJ/iU^^fitA-*-/^ \ A*XcA+aA(LX/, Low,)
40:60
Methyl isobutyl ketone r^rolupil *'
.
30:70
Hi-Flash solvent naphtha: turpentine
70:30
Methyl acetate: isopentane'
__
''Shell TS-281; xylene
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IV. AROCLOR AND CHLORINATED RUBBER. PLASTICS FILMS
The resinous AroclorJ 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: i/ParW': resin,
ratios./Similarly, the plasticizer type Arodor 1242,1254 and 1260 show good miscibility in chlori
nated 'rubber.
The properties of films derived from the following formulations containing either Parlon and resinous
Arodors 1262 or 5460, or Parlon andthe plasticizer type Arodors 1242,1254 or 126600 wwere--e studJie-dJ.
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KEMH8US TVPB rtnOOLfflP,. FOR PARLON PLASTICS
Ingredient^
*
,lParlori/20-cp........................................................... 1616 Arodor 5460............................................................ 8 g Dibutyl pnthalate.......................................
Tung oil, Thermolyzed, 976.................
Xylene or butyl acetate......................................7676
Parts by weight
16 16 12 12 8 8 12 12
43 5
7* 7* 7 73
12 12
3-75 71.25
PLASTICIZER TYPE AROCLOR0 FOR PARLON PLASTICS
Ingredient/
Parts by weight
'^PPaarlroino,iii20-cp...........................................................20
20 20
as` r 1254 or 1260............................................... 4 ylene...................................................................... 76
7 20 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 Arodor 5460 gave good adhesion to aluminum, bare sted, primed sted, galvanized iron and 'Transit?1' surfaces. Other commercially available resins, particularly oil-
modified alkyd resins, tested in similar films gave better adhesion than Arodor 5460 to such
surfaces as glass, tin, copper, sealed wood and qgllophane.
,(
The lacquer films plasticized with Arodonl 1234 or 1260 gave good adhesion to Transits, cello
phane, galvanized iron and primed sted surfaces. Some of the other commercially available
plasticizers tested in similar films gave better adhesion
to aluminum, tin,
w > pare sted, copper and sealed wood surfaces.
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Aroclorffalonej possess pronounced adhesive qualities.
mlwivihq objective is to
produce adhesives, by varying the Arodor content or by using a mixture ofArodorf 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 SolutionsArodors 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 cent hydrochloric add, 5 per cent sodium hydroxide, 5 per cent sodium chloride
solutions and to water spot tests.
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Film Hardness:-- Using Arcelor 5460 in ratios of 5: 10 and xo: 20, A#octor ; Bairlon, deddely softer film* were produced than when other commercial resins were similarly used. Likewise, Aroclors 1254 or 1260 used in ratios of 2:10 and 5 : io,'Xroclof: 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.
Cold-Check Resistance:-- Regarding cold-check resistant qualities imparted to chlorinated rubber films, Aroclor 5460 is somewhat superior to Bakelite type resins, but not as good as long-oil modified alkyds. Aroclor 1260 used as a plasticizer rates, in terms of cold-check resist ance, 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 containing Aroclors 5460, 1254 or 1260 have entirely satisfactory sanding and polishing characteristics.
Weatherability:-- Pigmented chlorinated rubber finishes containing Aroclors have consistently shown good outdoor weatherability. 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 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:
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 IV.
TABLE IV. AROCLOR PLASTICIZER IN CHLORINATED RUBBER PAINTS
FOR ALKALINE SURFACES
Materials
(Examples of starting formulas)
Formula 1 for basement floors
Formula 2 to meet Fed. Spec, TT-P-91
(Parts by weight)
, jt-i Formula 3 for swimming pools
'`Parlon, 20-cp. type..................... . . . .
Aroclor 1254
/j
"Rezyl 869' Arodor 5460 orCumar Yio"C*4*
*Beckosol 31M
.
Tung oil, Thermolyzed, 976 . .
Titanium dioxide.........................
Zinc oxide......................................
Silica flour...................................... Carbon black..................................
Xylene.............................................. .... Hi-Flash naphtha.........................
Totals..............................
18
3 42.8
18 10,
6
16 2
-5 47*5
xoo
14.6 44
*- 2.9 44 197 6-5
47-5 xoo
B. Acids and Alkali-Resistant Finishes:
Particular care must be exercised in the choice of resins and plasticizers for use in chemical resistant paints. For this purpose, Aroclors are outstanding and are being used successfully in the add and alkali-resistant chlorinated rubber formulations given in Table V.
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For interior use against
/ adds and ) C alkalies /
, /Parlon, 20-cp. type.....................
16
Arodor J4<o.................................. . 6-4 ,7Bakdite XJ-12895". (BtMMJbt. Q> \
MRezyl Rof'(solids).......................... Arodor 1254..................................
8
Arodor 1260.................................. Tung oil, Thermolyzed, 976 . . Iron oxide...................................... Titanium dioxide......................... Zinc oxide......................................
l6
Zylene.............................................. Hi-Flash naphtha.........................
53-6
Toluene..........................................
l6
M 4.8 4.8 16
51
16 -4 4-8 4.8 l6
5*
18
8 6 18
39
II
12 6
7-7 18 6 28 10.3 12
Totals .
Thete'p'paaiinntls ,,
wcre a.p.plied to metal bars or .panels and testedTPormula
.ABWt, showed ggod resistance to a 10 per cent hydrochloric add nWift and'tVfr 5 per cent sodium
hydroxiddajfBBnfe^rhe add resistant paint described under the heading of Formula 2 ' '
excellent outdoor protection 40 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 including glass.
Paint based on Formula 5 is indicated to have good resistance against warm aqueous solutions
rung soap.
>uld be pointed out that Aroclor and chlorinated rubber finishes are not recommended for
iuous exposure at temperatures above 140?.
C. Marino Finish**:
f~
Arodor plasticized chlorinated rubber coatings possess good resistances salt water and their hard finish deters algae and marine growil^iMPmlliiilBffgalimmi rflikTVtffliae* and good chemical
resistance indicates the usefulness of these paints to protect wood and metal used in making boats, barges and other marine equipment. A suggested formula for a marine paint is given in TablejbiL
TABLE W. QBSSga&BBnammm FW a chlorinates rubber MARINE white paint (Starting formulation)
Materials . _
Parts by Vight
Parlon, 20-cp. type7........................................................................
20
Aroclqr 1254......................................................................................... "Rezyl 869".............................................................................................
6 6
Titanium dioxide . ............................................................................
25
Xylene............................................. Hi-Flash naphtha ................................................................................
23 , 20
. Total..................................................................................... xoo
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Emulsion Paints:
Aroclgr 1254 is used in dftorii
rubber emulsion paints
lical resistance
on porous sur&cesVHeiailes Powder Company reportfthat preferred water phases
>r such paints are either a 1 per cent solution ofAerosol OTin distill* water or a 4 per cent solu-
don of sodium oleate in distilled water. For the awnp_li__
, ratio by weight of lacquer
phase to water ppihaso^f^m-iiT4ssmuggestedrParlonh oc f an_y desired viscosit_y .ma.y be used. A typical
paint phase for the Axodor-Parlon emulsion paint contains the following ingredients:
PAINT PHASE FOR THE EMULSION
Ingredients
Parts by weight
"Pulon'.'........................................................... ..................................... 'Arcelor 1254.....................................
28 14
'Cumar Pro.............................
10
Xylene . . . ...................................................`.............................. Hi-Flash naphtha......................................................................
24 24
Total...............................................................
100
E. AdKaalvaa:
1
(g^BgftPBid chlorinated rubber adhesive^ art t--iwaat tu tiiwt--fo^mfrwere developed originally 'Tofadbering labels to add btJftles. These adhesives are also of unusual interest becausen>f their good
fire resistant qualities. A typical formulation contains the following ingredients:
Ltgrcdients
L FOR CHLORINATED RUBBER ADHESIVES Ram by weight
:::::::::::::::::::
Aroclor 1260............................................................... .........................
1 6
Toluene.................................................................................................
68
>
Total.....................................................................................
too
F. Paper and Textile Coatings:
Aiodor 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
rinated rubber finishes would seem suitable for certain fabrics used indoors, but not wWKt expos&^ffr high temperatures and direct sunlight--
O. 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 protea electronic equipment against both moisture and fungi. Moreover, the fire resistant qualities of these plastics are nighty 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 CHLORINATgg RUBBERg^a
* The resins and plasticizers given in ihui fWlliiiwiij, Table VII artSSSfoWriW chlorinated rubber. This was determined by the examination of films laid down from 2: i.and 1:1, 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
^WjetdDsoi, 806P, ST-137, F7('M-~J*- *'FormvaiY. fMhP+
\
dor 1262, 5460
CUelva*e.5 (
--*1*^ f/i><SLu-<X^ <y>* ~f' )
?20,930,935,940 [X.%,
, CiioO'CIyptal 1247,2450,2454,2458,2464,2466,2500' (G.
BakeEteIVRD_-3i>iO8on, VXRD-4.i5m03i, XVRD-.4jn0n0<6,
. 'f''iLre__w_i1s__o1l 2_TL, .2a8, .3.3i*i' fr n . /) . e- ^.
BR-2963, XJ-9868, BR-1329, BR-3360
Methyl Methacrylate Polymers
.J
)
'
' Beck.umne P-.38, P-254 G, M, X"
^ &.)
1 Beetle*Resin 227-8 '' Clorafin 70" f
?4< 5- t9' _ 4^
^HRczylTl6, X315, 412, 775, 803, 807, 829, *69, '' ) 880,1103
Rosin .
.
0*a4^U#4<^ r^w^cv-C j)
East India gum Ester gum Ethyl Methacrylate '<^tero}tf5o (J.,
Amylchloro naphthalene Amyl oleate Amyl stearate Aroclor iiai Aroclor 1254 "Aroclor 1260 Butylmyristate Butyl stearate Camphor Castor oil, raw Castor oil, dehydrated Castor oil fatty add esters '1 Cellosolve'^hthalate Coconut fatty add esters Diamyl naphthalene Diamyl phthalate Dibutyl phthalate* Dibutyl sebacate Diethyl phthalate ** Dimethyl phthalate*1*
*'Hcrcolyn*' ( Linseed oil
tf^^^yntex Hi, H3, H12,17, 213, 22, 28, 29,32, tfA&M't G.)
**7^Teglac 15, Z-152 " (&*h . <&***
'"
`Velsiool AD6-31 v '1 Vinsol>
+ &,)
PLASTICIZERS
l; Methyl cellosolve oleate 1
^ Monoaqiyl naphthalene .
\
Naftotap ' ( uJ j)
" Nevffleneavy oil No. 2 ^
1
M Nevillite'oil (c
. J
"yj -- Oitidca oil
Palm fatty add esters ? --Perjllaoil------ ^
-*--
sr
Polyamyl naphthalene Resinous Products C-24 Santidzer B-16 b*>fvl
. . . . . 1 +. \
butyl 7 7
,
Santidzer*M-l7 (
a^jy|
Sextol phthalate
<
Sextol stearate
Soya bean fatty add esters
Soya bean oil
.
^Thermoil A," C
Tributyl phosphate
n QJL
Tricresyl phosphate**
Triethyl dtrate
Triphenyl phosphate **
Tung oil, Thermolyzed, 976
<?+*/! <j(rc 0 1 ^
^. n Q
The strong points and limitations of the resins and plastidzers 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
Prnrioor to Wwoorod Wwar 1I1I /Avrocliort*^,uussecdu in bsuubosstuaunituiaul uamououuunti witiah uchuluonriunaticeud rubobuecri, rmaadu
growth in the applications given in this report. During the war, scarcity of natural rubber ci
these developments but since the war industry has been quick to resume the use of Atock
.tici!z_ejd *c1h.1l_o_ri!n_a_te_dar_ubber compositions.
_____ /
Their principal field of application is as lacquers, varnishes and paints where flame resistance, cor rosion resistance, chemical resistance, i.e., resistance to acids, alkalies and water, and good electrical insulating properties are required.
When properly pigmented these paints or coatings have good weatherability. Although the adhesion of unplasodzed chlorinated rubber films to common structural materials is poor, when plasticized with Arodors strong adhesive bonds are obtained. Aroclors improve the flexibility and life of chlori nated rubber plastics, coatings.
e/formulations mAroclorf and chlorinated rubber along withmem|uggest^^es^ as riven in this
report/ wdiTtffi
commercial practice. Much of the aM^iw'wa^obtamed from other
a p*
firm*s* , particularly UHea.r-c_u.1lems lP>Aowniidle*r PCAommip.aanny, WWiillmmiinnogttAoini , tDVelalatwmarr*e, TThhe if--rrfffioi --imfaciliiioinii igilnijiaant-rhfrarriui
is \0 erve as a guide or starting point in the development of formulations to expand taking advantage of
the outstanding qualities of Arodors as resins and plasticizers for chlorinated rubber.
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A
-------- /
Monsanto
Chemicals "Plastics ____
For further information about AJ?OCi.OR$, write# wire or coll the nearest Monsanto office.
MONSANTO CHEMICAL COMPANY
ST. LOUIS BIRMINGHAM . BOSTON CHARLOTTE CHICAGO CINCINNATI CLEVELAND DETROIT LOS ANGELES NEW YORK PHILADELPHIA PORTLAND (On.) SAN FRANCISCO
MONSANTO (CANADA) LTD. Montreal
Representative! In the Principal Cities of the World.
020A67*)
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