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Preliminary Technical Bulletin Onalon R-7611
by; Robert N. Garlick April IS, 1969
MONSANTO COMPANY HYDROCARBONS AND POLYMERS DIVISION
RESEARCH DEPARTMENT SPRINGFIELD, MASSACHUSETTS
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1.
INTRODUCTION
Opalon R-7611 is a Btir-in foamable paste resin developed to meet the needs of the molding, flooring, and coating industries. The superior rheological properties along with excellent physical properties and foam quality make this resin ideal for applications such as;
1. Coated Fabric
a. outer wear
b. hand bags c. upholstery
2. Flooring Foam Layer
3. Slush Molded Footwear
4. Foam Sheet
5. Carpet backing pad
Typical Resin Properties Polymer Specific Viscosity Maximum Heat Loss Appearance Bulk Density Average Particle Size
FVC homopolymer 0.42* 0.3% White Powder 15 lbs./ft.3
2.0-3.0 u
*0.40 grams resin in 100 ml. cyclohexane - measured at 25C
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RHEOLOGICAL PROPERTIES
Viscosity
The rheological properties of Opalon R-7611 are superior to all
competitive resins tested. Figure I shows the viscosity of several
resins in a high plasticizer formulation. Figure II is a similar
plot for the same resins in a low plasticizer system.
Low Plasticizer Formulation
High Plasticizer Formulation
Resin
Dioctyl phthalate (DOP)
Santicizer 160
Paraplex G-62
Dyphos* (National Lead)
Azodicarbonamide*
paste (50/50 powder in DOP)
FIGURE I Apparent Viscosity of Plastisols
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In the high plasticizer system, R-7611 is competitive in the lower shear rate range and superior in the higher shear rate range, Opalon Jl-7611 also shows no dilataney.
FIGURE II Apparent Viscosity of Plastisols
In the low plasticizer system, R-7611 has the lowest viscosity at ail shear rate ranges, and is better by a factor of two. The superior flow properties of R-7611 will allow faster coating speeds and a smoother surface. Processes requiring high shear pumping will experience a lower heat build-up. yisoositv Aging The following table shows the viscosity aging in '60 phr DOP formulation. The magnitude of the viscosity is again substantially less than the competitive foam resins tested, and the percentage increase after 7 (lays is the least with Opalon R-7611.
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TABLE I Viscosity Aging (25C) HAT Brookfield Viscometer, 20 rpm, centipoises
2 hr.
24 hr.
7 day Percent Increase (7 day vs. 2M hr.)
R-7611 8800
11600 17800
102%
Resin A 13300 19000 29000
123%
Resin B 10900 17200 29800
128%
Resin C 22300 29000 98000
115%
Good viscosity aging is of prime importance for the compounder who frequently encounters high temperatures in storage, warehousing or trucking. Batch ends may be stored for longer periods of time resulting in substantial savings for the processor.
Filled Formulations Since fillers are widely used in foam applications, the flow behavior of atomite filled systems was investigated. A CaCO^ loaded system with Opalon R-7611 again had an unusually low viscosity and proved itself superior to competitive foam resins.
Resin D0P Atomite Stabilizer
100 100
50 2
.
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TABLE II
Viscosity of Filled Plastisol (cps)
Brookfield; S rpm 50 rpm
Severs; 90 psig
R-7611 10740 3776 2998
Resin A 29120 8000 4012
High filler loading and subsequent reduction in formulation costs can be attained with Opalon R-7611 without adversely affecting rheology. Fillers can, however, have a detrimental effect on foam qyality so that no more than 25 phr are recommended where optimum physical properties are desired.
Pigmented System
^
The effect of TiO^ was also checked in the following formulation.
Opalon R-7611 again had a superior viscosity by a factor of two. A minimum viscosity will aid in eliminating entrapped air and flow marks caused by the coating blade or roll.
Resin OOP Santicizer 160 Dyphos* Azodicarbonamide* TiOg (rutile)
100 25 25 4 4 5
*paste (50/50 powder in POP)
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TABLE III
Viscosity of Pigmented System (cps)
R-7611
Resin A
Resin B
Brookfield; 5 rpm
22400
128000
41200
20 rpm
16960
68800
28500
50 rpm
14912
50240
25600
Severs; 50 psig
41300
59800
70700
It should be noted from the studies on rheology that Opalon R-7611 has a substantially lower viscosity than the competitive foam resins tested and is superior in overall rheological properties. These advantages can be utilized by any application in which flow is important.
1
T e n sile S trength (p s i)
PHYSICAL PROPERTIES
Using the high plasticizer formulation (page 2) thin films (24 mis) were made at 195C at various times. The tensile strength of the^samples
was determined, and is plotted in Figure III versus the foam density.
FIGURE III
180 Tensile Strength vs. Foam Density Resin C:
160 A- Resin A
140
120 & 5 min. @ 19SC 7.5 min. @ 195C
100
18 19 20 21 22 23
Density (lb./ft. )
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When compared at an equal density, Opalon R-7611 has a higher tensile strength. This plot also demonstrates that Opalon R-7611 has a lower ultimate density for a given time of exposure at 195C.
Other physical properties included in the evaluation were compression set (the set after being compressed to one half its original thickness for 22 hrs. at 22C), compression resistance (the load necessary to compress the thickness 50%) , percent elongation and 100% elongation.
The data is shown in Table IV, including the density at which the properties
were evaluated. The properties of Opalor. R-7611 would have improved if
evaluated at a density equivalent to the competitive resins. In all cases
Opalon R-7611 was shown to be competitive or better than the commercial
foam resins tested.
Compression Set Compression Resistance Percent Elongation 100% Modulus Density
Table IV
Average Physical Properties
R-7611 15 psi 29 psi 160% 169 psi , 14.9 lb/ft'
Resin A
. 15 psi
30 psi
155%
152 psi 16.4 lb/ft
3
31 psi
156%
154 psi 16.6 lb
Resin C 14 psi 31 psi
120% 144 psi 16.9 lb/ft
HEAT STABILITY
The basic heat stability of Opalon R-7611 was compared to commercial foam
resins. Stabilizers normally used in foam formulations such as Synpron 936
(Synthetic Products Co.), Advastab ABC-2 (Advance), Mr)k 552 (Argus Chemical
Co.) , and Dyphos (National Lead) were tested in the fr ?lowing non-foam
formulation.
Resin
100
DOP 60
G-62
5
Stabilizer
.
2
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Time 19SC
Synpron 93G 5 min.
10 IS 2S
Advastal) ABC-2 5 min.
10 IS 2S
Mark S52 S min.
10 IS
Dyphos S min.
10 15
TABLE V Heat Stability of Opalon R-7611
R-7611
Resin A
Resin B
clear light yellow yellow yellow
clear clear yellow orange
clear clear yellow orange
8.
Resin C clear . light yellow yellow orange
clear light yellow black black
clear light yellow black black
clear
light yellow
yellow
black
cl ear light yellow black bl ack
clear clear black
clear clear black
clear clear black
clear clear black
white light tan tan
white tan brown
white light tan tan
white 1 ight tan brown
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H FOAM QUALITY
Foam samples of the four resins in both high and low plasticizer formulations were made by heating at 19SC. Various oven times were used. The cell structure of Opalon R-7611 is superior to the other resins at 8 and 10 min. in the high plasticizer formulation. Figure IV shows samples of Opalon R-7611 and a widely used foam resin. When exposed for times longer than 10 min., all the resins began to degrade.
FIGURE IV
Foam Resin
The use of Opalon R-7611 will consistently result in a foam having fine, uniform cells and good color.
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i
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STABILIZER SELECTION The excellent foam quality (i.e., cell structure, surface and color) of Opalon R-7611 shown in Figure IV is the result of a properly balanced formulation. The foam quality of expanded vinyls is actually determined during the heating cycle when the plastisol is in the "melt region". The selection of a stabilizer which causes decomposition of the blowing agent at the optimum temperature is the critical factor in obtaining good foam quality.
The variation of melt viscosity with temperature for a plastisol will be fixed for a given formulation, whereas the decomposition rate and decomposition temperature of the blowing agent will vary with the type and level of stabilizer selected. This is the most important variable available for improving foam quality. The properties of some stabilizers which give good foam quality "with Opalon R-7611 arc shown in Table VI. The active ingredients of each stabilizer are shown in Table VII.
Each stabilizer produces optimum foam quality under a fairly narrow set of conditions as specified by the melt viscosity of the plastisol. Both decomposition temperature and decomposition rate of the blowing agent-stabilizer system must be considered. In general, a plastisol with a higher fusion temperature requires a stabilizer which activates decomposition at a higher temperature. A high melt viscosity requires the use of a stabilizer producing a slow decomposition rate. The best combination of stabilizer properties for use with Opalon R-7611 is an intermediate decomposition temperature Find a moderate decomposition rate For most plastisols based on Opalon R-7611. fcdvastab ABC-1 and ABC-2, Ferro 5373 and Ferro 5473, and Nuns table V-1026 are recommended. The actual stabilizer used will depend on the melt viscosity of the complete formulation.
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There are some other factors to consider in selecting a stabilizer. 1. Lead stabilizers can have a detrimental effect on the foam color by increasing susceptibility to "sulfur staining". Zinc stabilizers work equally well and do not cause this problem.
2. The stabilizer must be well dispersed to obtain the best results.' Liquid stabilizers are easier to disperse, as well as handle, and may eliminate a potential problem.
3. The processing conditions such as dwell
time, oven temperature, and oven air
velocity all affect the heating rate of .
;]
the plastisol. It is suggested that several
"
stabilizers be run through the processing line
:i to determine the optimum one for the formulation.
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]
1
Stabilizer
1 Advastab ABC-1 Advastab ABC-2 Dyphos
1 Ferro 5373 Ferro 547 3
Nuostabe V-1020
1 Mark 552
Foam Density
16.3 lb/ft3
17.7 18.7 15.8 16.5 15.9 17.5
TABLE VI
111 ow-Up Rati o
4.4 4.1 3.8 4. 6 4. 4 4.6 4.1
Color ^
7.8 5.7 5.5 9.4 1.0 5.6 0.0
Decomposition
Temp.
Rate
.1 80 C 170 164 170 177 182 .177
Moderate Moderate Fast SJ ow Moderate Moderate Fast-Moderate
1 ^Col or eyo com elation X* - Z* x 100 (The higher the figure, the Y* whiter the foam color)
X* = 0.085 X Y* = 0.875 Y Z* = 1.023 Z
formulation
Opalon R-76.1.1 DOP Kempore 125 Stabi]izer
100 60 2 2
TABLE VII
Stabi] ixor
1 Advastab ABC-1 (Advance' Div. , Cal'] is] c Client. Co.) Advastab ABC-2 (Advance Div., Carlisle Chom. Co.) Dyphos (National. Lead Company) Ferro 5373
1 (l'erro Corporation) Ferro 5473 (Ferro Corporation)
1 Nuostabc- V-1026 (Nuodex Division) Mark 552 (Argus Chemical Corporation) .
1
Active Ingredients Modified Liq. Zu
It tt tt
Dibasic 3 cad phosphite Liq. Pb-7m, organic inhibitor Liq. 7m, " " Liq. Pb complex Modified Liq. Cd-Zn
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Recommended Formulations The following formulations are suggested starting points for typical uses of vinyl foam resin.
Coated Fabric
Upholstery
Opalon R-7611 DOP Santicizer 160 Paraplex G-62
Ferro 5375
Atomite
Kempore 125
Outerwear
Opalon R-7611 DOP Santicizer 160 D0A Paraplex G-62 Advastab ABC-2 Ti02 Kempore 125
Flooring
Opalon R-7611 DOP Santicizer 160 Paraplex G-62 Mark 552 Ti02 Kempore 125
Carpet Backing
Opalon R-7611 DOP Santicizer 160 Paraplex G-62 Advastab ABC-2 Kempore 125
100 45 35 5
2
40
2
100 45 45 10 5 3 5 3
100 25 25 5 2 5 3
100 62 29 5 2 3
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