Document 06qyBz0aY7grnBqYgKpVZmZ6n

TOWOLDMON0039595 WATER_PCB-00024064 JRV * Preliminary Technical Bulletin Qpalon R-7611 by! Robert N. Garlick April IS, 1969 MONSANTO COMPANY HYDROCARBONS AND POLYMERS DIVISION RESEARCH DEPARTMENT SPRINGFIELD, MASSACHUSETTS 0623891 TOWOLDMON0039596 WATER_PCB-00024065 1. INTRODUCTION Opalon R-76I1 is a stir-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 M. Foam Sheet S. Carpet backing pad Typical Resin Properties Polymer , Specific Viscosity Maximum Heat Loss Appearance Bulk Density Average Particle Size FVC homopolymer 0.H2* 0.396 White Powder 15 lbs./ft.3 2.0-3.0 u *0.40 grams resin in 100 ml. cyclohexane - measured at 25C O623091 .01 TOWOLDMON0039597 WATER PCB-00024066 2. KJIKQIXXjTCAI, 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 11 is a similar plot for the same resins in a low plasticizer system. Low Plasticizer Formulation High Plasticizer Formulation Resin 100 100 Dioetyl phthalate (DOF) 2S 45 Santicizer 160 25 45 Paraplex G-62 5 .5 Dyphos* (National Lead) 4 4 Azodicarbonamide* 44 paste (50/50 powder in DOP) FIGURE I Apparent Viscosity of Plastisols Apparent V is c o s ity (p o is e s ) TOWOLDMON0039598 WATER_PCB-00024067 3, In the high plasticizer system, R-7611 iB competitive in the lower sheer rate range and superior in the higher shear rate range, Opalon R-7611 aleo shows no dilatancy. FIGURE XI Apparent Viscosity of Plastisols In the low plasticizer system, R-7611 has the lowest viscosity at all 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. Viscosity Aging The following fable 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 days is the least with Opalon R-7611, .. `' ' 0623893 TOWOLDMON0039599 WATER PCB-00024068 TABLE I Viscosity Aging (25"C) HAT Brookfield Viscometer, 20 rpm, centipoises 2 hr. 2*1 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 ( 22300 29000 98000 11 S% 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 CaCOj 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 BO 2 0623894 TOWOLDMON0039600 WATER_PCB-00024069 5. L P t C r" L 6 TABLE XI Viscosity of Filled Plastisol (cps) Brookfield; S rpm R-7611 10740 Resin A 29120 50 rpm Severs; 90 psig 3776 2998 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 EOF Santicizer 160 Dyphos* Azodicarbonami.de* TiO^ (rutile) 100 25 25 4 4 5 :paste (50/50 powder in D0P) 0623895 TOWOLDMON0039601 WATER_PCB-00024070 TABLE III Viscosity of Pigmen ted System (ops) R-7611 Resin A Resin ] Brookfield; b rpm 22400 128000 41200 20 rpm 16960 68800 28500 50 rpm 14912 50240 25600 Severe; 50 pslg 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. PHVSICAL 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 TpncJlp RtrerurHi vs. Foam Density T ensile S trength (psi] 18 19 20 21 22 23 Density (lb./ft.^) . 0623896 TOWOLDMON0039602 WATER_PCB-00024071 ] J When compared at an equal density, Opalon R-7611 has a higher tensile strength. Ihi6 plot also demonstrates that Opalon R-7611 has a lower ultimate density J for a given time of exposure at 195'C. j Other physical properties included in the evaluation were compression set (the set after being compressed to one half its original thickness for 22 i hrs, at 22C), compression resistance (the load necessary to compress the 1 thickness 50%) , percent elongation and 100% elongation. The data is shown in Table IV, including the density at which the properties J were evaluated. The properties of Opalon 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. Table IV Average Physical Properties R-7611 Resin A Resin B Resin C Compression Set 15 psi 15 psi 25 psi 14 psi Compression Resistance 29 psi 30 psi 31 psi 31 psi Percent Elongation 160% 155% 156% 120% r 100% Modulus Density k. 169 psi 14.9 lb/ft3 152 psi , 154 psi 144 psi 16.4 lb/fe 16.6 lb/ft3 16.9 lb/ft3 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), Mok 552 (Argus Chemical Co.), and Dyphos (National Lead) were tested in the following non-foam formulation. l Resin DOP G-62 Stabilizer 100 60 5 2 0623897 TOWOLDMON0039603 WATER_PCB-00024072 Time @ 19SC Synpron 93G 5 min. 10 IS 2S Advastal) ABC-2 S min. 10 IS 2S Mark 552 S min. 10 15 Dyphos S min. 10 IS TABLE V Heat Stability of Opalon K-7611 R-7611 KeBin A Resin B clear light yellow yellow yellow clear clear yellow orange clear clear yellow orange B. Resin C clear . light yellow yellow orange clear lij^it yellow black black clear light yellow black black clear light yellow yellow black cl ear light yellow black black clear clear black clear clear black clear clear black clear clear black white light tan tan white tan brown white light tan tan white 1ight tan brown 0623898 TOWOLDMON0039604 WATER_PCB-00024073 9. 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 * XV 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. 0623899 TOWOLDMON0039605 WATER_PCB-00024074 10. STABILIZER SELECTION The excellent foam quality (i.e., cell structure, surface and color) of Opalon K-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'1. 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 i a slow decomposition rate. The best combination of stabilizer properties for use with Opalon R-7611 is an intermediate decomposition temperature and a moderate decomposition rate l'or most plastisols based on Opalon R-7611. Mvastab ABP-1 and ABC-2, Ferro 5373 and Ferro SM73, and Nnostublo V-.1U2G are recommended. The actual stabilizer used will depend on the melt viscosity of the complete formulation. i 0623900 TOWOLDMON0039606 WATER_PCB-00024075 11. 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 to determine the optimum one for the formulation. I TOWOLDMONOQ39607 WATER_PCB-00024076 ] 32. ] 1 Stabilizer 1 Advastab ABC-1 Advastab ABC-2 Dyphos 1 Ferro 5373 Ferro 507.3 Nuostabe V-102G 1 Mark 552 Foam Density ]G.3 lb/ft3 ] 7.7 3 8.7 35.8 10.5 15.9 37.5 TABLE VI B1ow-Lp Rati o 4.4 4.3 3.8 4.6 4.4 4.6 4.3 Color ^ 7.8 5.7 5.5 9.4 1.0 5.6 0.0 Decomposition Temp. Rate ,i Rnc 170 164 170 177 3.82 .1 77 Moderate Moderate Fast SJ ow Moderate Moderate Fast-Moderate 1 ^Col or eye correlation X* - Z* x 100 (The higher the figure, the Y* whiter the foam color) 1 X* = 0.685 X Y* - 0.875 Y Z* = 1.023 Z formulation Opalon R-763.3 DOP Kemporo 125 Stabi]izer 100 60 2 2 TABLE VII Stabi] jy.or 1 Advastab ABC-1 (Advance Div. , Carlisle Chcm. Co.) Advastab ABC-2 (Advance Div. , Carlisle Chain. Co.) Dyplios (National. Lead Company) Ferro 5373 1 (l'crro Corporation) Ferro 5673 (l'erro Corporation) 1 Nuostabo V-1026 (Nuodex Division) Mark 552 (Argus Chemical Corporation) . Active ingredients Modified L i (j. Zu It tt tt Dibusjc lead phosphite L.i(j. Pb-Zn, organic i Jiliibi.tor Liq. Zn, " 11 Liq. Pb complex Modified Liq. Cd-Zn 0623902 TOWOLDMON0039608 WATER PCB-00024077 Recommended Formulations The following formulations are suggested starting points for typical uses of vinyl foam resin. Coated Fabric Upholstery Opalon R-7611 OOP 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 A 1.U^ Kempore 125 Carpet Backing Opalon R-7611 DOP Santicizer 160 Paraplex G-62 Advastab ABC-2 Kempore 125 100 46 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 0623903 TOWOLDMON0039609 WATER_PCB-00024078