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Monsanto
Chemicals`'Plastics
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AROCLOR
As Used in Chlorinated Rubber
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Ayx'^ > ,ftr7
an& Technical Bulletin I In.' P m-
January 1, 1948--
Monsanto Chemical Company,-^, Louis jf, MoP--
1/
--
AROCLOR^, chlorinated biphenyl and OoUOflBafMiMai poljr/phenyls, are effective plasti cizers and resins for chlorinated rubber base lacquers, varnishes and paints. These protective coatings are used s^pe flame resistance, corrosion resistance, chemical
resistancx|fi6pHBriMBBWi("adds, alkalies and water)?and good electrical insulating p perti ^
Some of the important applications for these protective and decorative coatings for wood, metal, brick, stone, concrete and fabric surfaces include: ' -/s
Wood and metal used
yachts, barges and other marine craft.
Structural steel for bridges, buildings, roofs and power-line structures.
Structural materials mmd at chemical plane, pulp and paper mills, textile mills,
petroleum refineries and gas works
k^protection against add fumes, alkalies
and
cars and other rolling stock and construction machinery against corrosive materials and weathering.
BPK&9 Equipment used in electroplating and as stop-off lacquers in this industry.
Masonry floors and walls. Concrete swimming pools and traffic paints.
A {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.
*AROCLOR*Reg. U.S. Pat. Off.
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DSW 305398
STLCOPCB4069552
aroclor! 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'lParlon.'1
Parlon isjnade by chlorinating natural rubbe^^Mntg" mixture of two polymers averagercnlorine content of 67 per cent.
an
PROPERTIES OF CHLORINATED RUBBER
The typical properties of*!Parlon 4s given by Hercules Powder Company, Wilmington, Delaware,
are listed in ilir finllmsTina, Table I:
.
TABLE I. TYPICAL PROPERTIES OF PARLON
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 ..................................... ... 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
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 ............................................. .... . 0.0015100.0030
Power factor at 25C. and 1,000 cycles, after immersion in water for 140
hours and surface wiped dry.................... ........................................ 0.0027
Mechanical (clear 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 elasticity, 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 ........ Effect of dry heat on film . . Softening point .......
nonflammable stable up to and at I25C decomposes at 135 to i50C.
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),
per cent..................................................................................... . . 0.27
Moisture vapor permeability of 0.003-inch film (grams water/
. square centimeter/0.01 centimeter/hour at 2iC.) .... 0.2 x to4
* Films used in tests were laid down from a toluene solution.
DSW 305399 STLCOPCB4069553
General resistance to:
:; i^
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 in Tabtrtlr
TABLE II. PARLON VISCOSITY TYPES
. Viscosity Type
Viscosity Range (in centipoises)
5-cp..........................................................
io-cp....................................................................
20-cp............................................................
5 to 7
8 to 12
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 given(L*fi-^A-tO
Type
Usi
5-cp. io-cp.
20-Cp. I25-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
flexibility^
Cbvvt
t tp /l t ty
Solvents and solvent mixtures suggested for use in preparingiAroclor and1 frarionyormuknons/tre
given in
Table III:
TABLE III. SljGGESlrfety SOLVENTS FOR AROCLOR ANEiPARLON (COMPOSITIONS tuff k 1
SOLVENTS'----- ----- ------------- J
'
,(Amsco Solv^B and E(
Amyl acetate
,
Butyl acetate
Carbon tetrachloride * Cellosolve1' CCeLrU^iitc
Diacetone alcohol
Diethyl carbonate Ethyl acetate
(1 Ethylene dichloride
.
</Hi-Flash''naphtha
Methyl acetate
Methyl ethyl ketone
.
Methyl isobutyl ketone
Methyl salicylate
t^Notol -- "7,
-
Octyl acetate .&.) "SovasoRNos. 74, 75
- \WUJ @J_ to A
` ^Solvesso 1000 "^5^
au)
'J
K^Tollac" /y,,.,:otn \
Toluene L
# ''Union Aromatic Solvent 3553-10
?0.^*'XJnion Solvent No. 30
' Xylene
.
DSW 305400
STLCOPCB4069554
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70:30
Acetone: hexane
97:3
Acetone,:mineral spirits
83:17
Benzene: isopentane
41:7:35 :17 'fcellosolve*: ethanol (anhydrous); ethyl acetate.-xylene
30:70
wCellosolve/': turpentine
'
18:59:23 ^teUosolve'iturpentine f mineral spirits
64:36
30:30:40 40:60
Ethyl acetate* isopentane
'
Ethyl acetate: isopropyl acetate: Troluoil ( Methyl isobutyl ketone :*Yiolu9il"
.
30:70
70:30 T.15
Hi-Flash solvent naphtha: turpentine
Methyl acetate: isopentane' ''Shell TS-28'; xylene
_1..................
a*,
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IV. AROCLOR AND CHLORINATED RUBBER, PLASTICS FILMS
The resinous Arodor^ 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/Parlorf': resin, ratios.TSimilarly, the plasticizer type Aroclor 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 andhthe plasticizer type Aroclors 1242,1254 or 1260 we^rje studied.
)r"pARLOn' PLASTICS
Ingredient^
*
1`Parlon1/20-cp.........................
16
Aroclor 5460.............................................................. 8
Dibutyl phtfralate.....................................
Tung oil, Tnermolyzed, 976.....................
Xylene or butyl acetate........................
76
Parts by weight
16 16 12 12 8 8 12 12
43 5
7* 7i 76 73
12 12
3-75 72.25
PLASTICIZER TYPE AROCLOR0 FOR PARLON PLASTICS
Ingredient^
Parts by weight
Parlon, 20-cp............................
.20
Aroclor 1254 or 1260 .........................................4
Xylene..................................................................... 76
20 7-
73
20 20 70
Examination of the films cast from these lacquers revealed the following characteristics imparted by
the Arodors:
`-
Adhesion: -- Unplasticized chlorinated rubber films have very poor adhesive qualities. The
lacquer film containing Aroclor 5460 gave good adhesion to aluminum, bare sted, primed steel,
galvanized iron and'Transitedsurfaces. 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 apllophane.
1,
The lacquer films plastidzed with ArodoOl 1254 or 1260 gave good adhesion to Transite, cello
phane, galvanized iron and primed sted surfaces. Some of the other commercially available
plasticizers tested in similar films gave better adhesion linn iIis'AujuJijh to aluminum, tin,
^ , bare sted. copper and sealed wood surfaces. Arodorgalonej possess pronounced adhesive qualities.
whi! it" thg Q^jecdve is to
produce adhesives, by varying the Arodor content or by using a mixture ofAitoclort 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:-- Arodors 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.
\ )
--5--
DSW 305401
STLCOPCB4069555
Film Hardness:-- Using Aroclor 5460 in ratios of 5 :10 and 10:10, Aiodor; Earlon, decidedly softer films were produced than when other commercial resins were similarly used. Likewise, Arodors 1254 or 1260 used in ratios of 2:10 and 5 : io,'Rfocl&: 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 plasticizer 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. Relativdy 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. Materials
AROCLOR PLASTICIZER IN CHLORINATED RUBBER PAINTS
FOR ALKALINE SURFACES
(Examples of starting formulas)
Formula 1 for basement floors
Formula 2 to meet Fed. Spec. TT-P-91
Formula 3 Car swimming pools
(Parts by weight)
18 14.6
. 10,
4-4
Silica flour.....................................................
3
Carbon black................................ ....
0.2
Xylene............................................................
42.8
Hi-Flash naphtha.............................................................
Totals............................................
100
6
16 2
o-5 47-5 100
2-9 44 19.7 6.5
47-5 100
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, 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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dS\N 305402
STLCOPCB4069556
'~jAtXl XZ
Vl w I t "f' / <*v't
Materials
--1 For interior
use against / adds and ) v. alkalies s
'' Parlorifzo-cp. type .... .
16
Arodor$46o . ..................... .
64
TjakdSte XJ-12895". (B+AUJz!.. &>)
MRezyl 8of'(solids) ..... .
Arodor 1254........................ .
8
Arodor 1260........................
Tung oil, Thermolyzed, 976 .
Iron oxide ........ . 16
Titanium dioxide................
Zinc oxide ................. .... .
' Zylene.................................... . 53.6
Hi-Flash naphtha................
Toluene................................ . - - ' "
2 For exterior
use against awls
For exterior
use against alkalies
For maximum resistance to
adds and alkalies
(Parts by weight)
16 16 18
64 4.8
4.8 16
64
4.8
4.8 16
8 6
18
52 52 39
11
Totals . ... . .
100
100
100
100
Foruse against
?P solutions
12 6
7-7
18 6
28 10.3 12
The'paints gUmiijUiilMaD were applied to metal bars or panels and tcstedTFonnula i| an interior
pni"* showe^ g9od resistance to a 10 per cent hydrochloric add jwtMNu and46^-5 per cent sodium hydroriddgjsBSHRjTThe add. resistant paint described under the heading of Formula 2 ha#=*k*Ti 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 induding glass. Paint based on Formula 5 is indicated to have good resistance against warm aqueous solutions
ining soap. buld be pointed out that Arodor and chlorinated rubber finishes are not recommended for Suous exposure at temperatures above i40F.
C. Maxine Finishes:
'~
Arodor plasticized chlorinated rubber coatings possess good resistance to salt water and their hard
finish deters algae and marine
flin/*1 ixniprinT1 u rflTjfTifi rianm. iTTt?'TVftfTliliiand 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 Table^QpDP
TABLE Vt. lAIUWLiLUILSagnWiHIP FOR A CHLORINATED RUBBER
Materials
MARINE WHITE PAINT (Starting formulation) '
Parts by hight
Parlon, 20-cp. type* Arodty-1254 . . . `fcezyl 869*1. . . . Titanium dioxide . Xylene . . . . . Hi-Flash naphtha .
20
$ 6
25 23 20
. Total . .
100
dSW 305403
STLCOPCB4069557
>:
! ; .V
-r-%
-** ^
: V - '
..................
. Emulsion Paints: 'y:.
..
Arodor 1254 is used in ddorirngted rubber emulsion paints mitasasadsdS&sjPcEemical resistance jgg5|riH*' n porous surfocesTlicrcules Powder Company ygportfthat Ms preferred water phases for such punts are either a 1 per cent solution ofAerosol OTin distilled water or a 4 per cent solu* don of sodium oleate in distilled water. For _the complete rmuhionj^- ratio by weight of lacquer
phase to water phasojSf^s to its suggested. Parioifofanydesircd viscosity may be used. A typical paint phase for the Arodor-Parlon emulsion paint contains the following ingredients:
PAINT PHASE FOR THE EMULSION
Ingredients
' Parlon................ 'Arodor 1254 . . , Cumar Pio Xylene . . . . . Hi-Flash naphtha
Total . ,
Parts by weight
. 28
14
.
~. 10
. 24
--Mtoo
E. Adhesives:
\
__ [Chlorinated rubber adhesives* ara rscistast. tothiaswaiw--dwere developed originally
loFadhering labds to add bdftles. These aahesives are also of unusual interest becaUseiof thdr good foe resistant qualities. A typical formulation contains the following ingredients:
'Parlon,'k25-cp. type 4rodor 1254 . . . Arodor 1260 . . . Toluene . . . . .
Total . .
FOR CHLORINATED RUBBER ADHESIVES
Parts by weight
20 6 6
68 100
F. Paper and Textile Coatings:
Arodor and chlorinated rubber coatings are worthy of consideration for specific end uses in the paper and textile ooatings 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 Arodor
anid chlorinated rubber finishes would seem suitable for certain faobrriics used` i'nd`oors, 'but not white
expose^fo high temperatures and direct sunlights
O. Coatings for Electrical Apparatus:
Because of their desirable electrical properties, compositions containing Arodors and chlorinated rubber are very useful to insulate and protect electrical wire and apparatus from moisture. When fortified with sdected fungistats and waxes, coatings of this type are used to "tropicalize" or protect dectronic 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:
Arodor plasticized chlorinated rubber compositions are very useful for printing inks where foster drying time 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 AROCLORi MISCIBLE IN CHLORINATgp RUBBER^^*
The resins and plasticizers given in thrifotiwwmg Table VII are mtstroia in 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.
..
.
fi 1
!
l
--8--
DSW 305404 STLCOPCB4069558
1C TABLE VII. RESINS AND PLASTICIZERS MISCIBLE IN PARLON
O
f
. RESINS - *-
-
.
____ji, 806P, ST-137, F7 (\
Arodor 1262,5460
; C'Gelva'^.s C
'f/\S>CCv-*Ck^s
)
VfcoplsSfeo,930,935, 940[X^. $*A*<,CWCft^Glyptsd 1247,2450,2454,2458,2464,2466,2500' (G,(b\
"BSEeIne'XR-3180, XR-4503, XR-4006,
Vewisol 2L, 28, 33 * r& \
'
BR-2963, XJ-9868, BR-I329j BR-3360 ^R*VUut<yMethyl Methacrylate Polymers
'
' Bwiadte 1112 "
Seville R-3, R-10 " CA/^CUU Cfw . <S> ,)
' Beckamnc P-iaS, P-254`TentalynA, G, M, X" CtU*^&^
" Qorafin 70" C{k^c^J2t^
i f^IC6WtD^
-'Jjjg*1103
-
^
ST]
Eastlndia gum *
Ester gum Ethyl Methacrylate
fJL ,
* 7 'YmL >4U*^Axyntex -Hl H3> Hi2> *7. 3 22, 28, 29,32,
^^-^Teglac 15, Z-152 " 1 'Velsicol AD6-3'1 C
j ^VinS01'' ^^
&>.)
Amylchloro naphthalene Amyl oleate Amyl stearate Arodor 1242 Arodor 1254 Arodor~i 260 ButyTmyristate Butyl stearate Camphor Castor oil, raw Castor oil, dehydrated Castor oil fatty add esters 1' Cellosolve'phthalate Coconut fatty add esters Diamyl naphthalene Diamyl phthalate . Dibutyl phthalate*Dibutyl sebacate Diethyl phthalate ** Dimethyl phthalate**
"Hercolyn'1 ((bAjudUa
Linseed oil
PLASTICIZERS
^Methyl cellosolve oleate J T.Monoaqiyl naphthalene . Naftolap* ( uJ
' Nevffleraavy oil No. 2 ^
.\ )
1
" Nevillite"oil 'yj) ,-Oitidca oil
. &J
"* Palm fatty add esters ,, f --Perjlla oil ---
. ,, a ,, - , n ~r ft r ~ l v' JxZXaJL c-tl*
Polyamyl naphthalene
Resinous Products C-24
... 1 1 1 +. \
Santirizer B-16 Ck>o1y[ phtkblyl
`f'f*'0
-Santidijr^M-17 (
^LHvJyl ffM/l <j \ c 1 ** *)
Sextol phthalate Sextol stearate Soya bean fatty add esters
'
Soya bean oil iThermoil A* C\J
Tributyl phosphate
.n QJL
s> \ ~ r> - -w^-O
Q
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.
DSW 305405
4-
Vv fti *v - .
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--9--
1 @e*w L>X, f&t, (fy
t. ^ f* x ( 1 v
L fo _ '
fp '
STLCOPCB4069559
V." ; vil. GENERAL
Prior to Word War II Arodori^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-7
tidzed 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. . ^
i -.
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 Arodors strong adhesive bonds are obtained. Arodors improve the flexibility and life of chlori
nated rubber ] ' '
'
<@efeon
and chlorinated rubber along with their suggested uses^as given in this
report i
w commercial practice. Much of the1'*1'' ` 'wasiibtamed fr^om other
particularly Hercules Powder Company, Wilmington, Delaware, The information giygdwo
is -jo serve as a guide or starring point in the development of formulations to expand taking advantage of
the outstanding qualities of Arodors as resins and plasticizers for chlorinated rubber.
rfc/PGS-SM-14t . (M-749-71
-- 10 --
DSW 305406 7rWWhUXJC
STLCOPCB4069560
--\f
Monsanto
Chemicals "`Plastics - ^/4_____
For further 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 (Or*.) SAN FRANCISCO
MONSANTO (CANADA) LTD. Montreal
Representatives In the Prindpql Cities of the World.
DSW 305407
STLCOPCB4069561