Document 9RZmmNRpoOYno7Xqj6LkpwER

RECEIVED OCT 9 5 1966 _ R. N Vheel r STATUS REPORT EXPLORATORY VINYL RESIN SCREENING EVALUATION OF QXOM-7 RESIN (BLEND 3) Author*! J. J. Brezinski J. W. Fields Dot*: June 1, 1966 Project No.: 399G10 File No.: 5757 SUMMARY Comparative evaluation of the QXOM-7 resin (Blend 3), which contains approxi mately 1.0 per cent ethylene and was prepared in production facilities at Texas City autocalves with a QYTQ-7 resin of comparable molecular weight reveals the following: Frocessibility Initial Fluxing The copolymer fluxes more readily than the QYTQ-7 resin in rigid and semi-rigid formulations. No significant differences in fluxing behavior were observed at higher plasticizer concentrations. Apparent Melt Viscoiity The torque requirements for compounds containing the ethylene copolymer were less through the entire plasticizer concentration range (10 thru 60 phr FLEXOL DOP). Surprisingly, no difference between the copolymer and homopolymer was observed in the rigid formulation. Physical Properties The inclusion of ethylene results in reduced tensile strength and room temperature stiffness dS well as increased elongation in both rigid and plasticized compounds. The vinyl chloride-ethylene copolymer requires approximately 5 phr less plasticizer than the homopolymer to achieve the same level of Shore hardness. Thus, the major advantage of the "O" resin are faster fluxing and lower melt viscosity in flexible compounds, internally plasticized nature which should permit use of 3-5 phr less plasticizer, and faster dry-blending character. Research and Development Department Chemical* Division Union Carbide Corporation ucc -2- INTRODUCTION This report discusses the physical properties and melt characteristics of a vinyl chloride-ethylene copolymer (QXOM-7 Blend 3) in plasticized and rigid formulations. The properties are compared to QYTQ-7 (Blend 130), a homopolymer of comparable inherent viscosity. The resins evlauated were prepared in Texas City production autoclaves using Process-7. The copolymer contains approximately 1 per cent ethylene with an inherent viscosity of 0.98. The inherent viscosity of the homopolymer is 1.0. DISCUSSION Plasticized Compounds Melt Charateristics The evaluation of the processing characteristics and the physical properties of the plasticized compounds of the vinyl chloride-ethylene copolymer (QXOM-7) and a poiy(viny! chloride) homopolymer QYTQ-7 were studied at 10 through 50 phr plasticizer level (FLEXOL plasticizer OOP). The formulations also contained 3.0 phr Mark M, a liquid barium-cadmium phenate stabilizer. These data are listed in Table III. The melt characteristics, shown graphically in Figures 1 through 4 may be summarized as follows. 1. The compounds containing the vinyl chloride-ethylene copolymer fluxes more readily at the 10 and 20 phr plasticizer level than the comparative homopolymer. No difference in time to initial fluxing could be detected in the 30 through 50 phr plasticizer level. However, the method used for this evaluation does not allow an establishment of fluxing times of less than one minute due to sample loading time (approximately one half minute) and the time for the plasti-corder to establish equilibrium (approximately one half minute after sample loading) . 2. The "O" resins exhibited slightly lower apparent equilibrium melt viscosity than the homopolymer counterpart through the entire plasticizer concentration range indicating that, in the same formulation, compounds containing the vinyl chloride-ethylene copolymer would process with lower power requirements. Thus, compounds containing vinyl chloride-ethylene copolymers require less dwell time in intensive mixers at the lower plasticizer concentration range and would process with less power requirements at all plasticizer levels. uce 039513 -3- Physical Properties of Plasticized Compounds The effect of the inclusion of ethylene on several physical properties may be summarized as follows: 1. Tensile strength is lowered, the rate of lowering of tensile strength with increasing plasticizer concentration is approximately the same for both homopolymer and copolymer. This data is shown in Table III, Figure 5. 2. The tensile elongation, as was expected, is increased in the compound con taining the ethylene copolymer. Again, the rate of increase with increasing plasticizer concen tration is approximately the same for both the homopolymer and copolymer (see Figure 6). 3. The brittleness temperature, shown graphically in Figure 7, is decreased an average of 3C over the plasticized concentration range by the inclusion of 1.0 per cent ethylene in the polymer. 4. Shore hardness, often used as a measure of plasticizer efficiency, is shown in Figure 8 to be lower in the QXOM-7 sample throughout the plasticizer concentration range. The data indicates that to produce a simple flexible compound with a Shore hardness reading of 85 would require 47 phr FLEXOL DOP for the QXOM-7 resin and 52 phr FLEXOL DOP for the QYTQ-7 resin. Thus, it would require approximately 5 phr less plasticizer for the ethylen copolymer than the homopoiymer. Previous data supports this observation (1). 5. Room temperature stiffness is also lowered as expected. Significant differ ences may be observed, (see Figure 9) in the semi-rigid compounds (10 and 20 phr plasticizer). The effect of the presence of ethylene in the resin decreases with increasing amounts of plasticizers. Rigid Compounds Although it is realized that the inherent viscosity of the resins evaluated restrict their use chiefly to plasticized formulations, this evaluation in a simple rigid compound was conducted to provide additional information on the influence of ethylene in copolymers. The formulation used contained 3.0 phr Mark WS, a powdered barium-cadmium stabilizer available from Argus Chemical Company. The data are shown in Table II. Physical Properties - Rigid Formulation 1. The tensile strength as was expected, is approximately 17% lower in the compound containing the ethylene copolymer than the one containing the homopolymer. TH Brezinski, J. J., Fields, J. W., Exploratory Vinyl Resin Screening: Evaluation of QXAM-11 Resin Samples QEX-1197 and QEX-1198 , Research and Development'Department, Status Report, File No. 4910, November 22, 1965. ucc 039514 -4- 2. The QXOM-7 resin is approximately 44% higher in tensile elongation than the QYTQ-7 resin. 3. Room temperature stiffness is lowered approximately 11 per cent by the inclusion of ethylene. 4. The addition of approximately 1% ethylene results in an approximate 17 per cent drop in heat distortion temperature at this molecular weight (64C vs 77C for QYTQ-7). Melt Characteristics - Rigid Formulation The study of the melt characteristics in a rigid formulation indicates a faster fluxing time (approximately 45 per cent) for the ethylene copolymer when compared to the QYTQ-7 homopolymer. No difference could be detected between the two resins in apparent melt viscosity. CONCLUSIONS Flexible Applications The inclusion of approximately 1 per cent ethylene at the 1.0 inherent viscosity range results in the following advantages over the homopolymer counterpart. 1. Faster fluxing time at the lower plasticizer concentration levels which should decrease residence time in intensive mixing devices. 2. Lower apparent melt viscosity which will decrease power requirement for processing and fabricating equipment. 3. An approximate 3C lower brittleness temperature over the plasticizer concentration range. 4. An approximate 5 phr better plasticizer efficiency rating. 5. Higher tensile elongation. This property indicates that film processed from ethylene containing copolymers would elongate a greater distance before film rupture or breakage occurs. The compromised physical properties are: 1. Lower tensile strength. The differences observed in this evaluation are not considered to be significant enough to exclude consideration of resins of this composition and molecular weight from flexible end product use. uc -5- Miscellaneous Property Evaluation Dry Blend Performance The copolymer resin (QXOM-7) dried approximately 60 per cent faster than the homopolymer (QYTQ-7) using the standard formulation and procedure. This faster dry blending characteristic is considered an advantage for the "O" resin. Hard Resin Particles The hard resin particles, as observed in a 10 mil flexible dyed film using a special test procedure presently under development are not considered to be sufficient to effect this resin for end product use; the resin contains a relatively low level of hard resin particl $. Particle Geometry The sieve analysis indicates a longer particle size for the copolymer and a desirable low fines content. Plasticizer Sorption The two resins tested are essentially equivalent in plasticizer sorption. Initial Color Mill Test (ICMT) The initial color of both resins are within the experimental error of the test as being the same. The QYTQ-7 sample exhibited better intermediate stability (color after 20 minutes processing) while the QXOM-7 exhibited better ultimate stability (less color after 30 minutes processing). NOTEBOOK REFERENCE: 20BAP-7237 PERIOD: April 15 to May 4, 1966 Attachments 3 Tables 9 Figures ucc 0395)6 -6- TABLE I EVALUATION OF VINYL CHLORIDE-ETHYLENE COPOLYMERS CHEMICAL AND GENERAL PROPERTIES QXOM-7 Blend 3 Inherent Viscosity^ WC-31-B-4 "08------ Ethylene Comonomer, % 0.9 Heating Loss, %j. WC-160-H Apparent Density, lbs/ft^; WC-2-1 99.8 29 ASTM Flow Time, seconds/400cc; ASTM D 1895-6IT 3.0 ASTM Plasticizer Sorption, %; ASTM D 1755-60T 97 Sieve Analysis; WC-7-F % Thru 40-mesh 100 60- mesh 98 80-mesh 46 100-mesh 18 140- mesh 3 200- mesh 2 Median particle size, microns 181 Dry Blend Test (Plasti-Corder) Time to Dryness, minutes 3.3 Temperature at Dryness, .C 79 Hard Resin Particles, 10 Mil Film; (1) 110 Initial Color Mill Test (ICM1); WC-163-C 121 20 Minute Holding Power, % 77 30 Minute Holding Power, % 72 QYTQ-7 Blend 134 1.00 99.8 31 3.7 95 100 100 97 80 8 5 126 8.0 84 120 122 86 62 (1) Test under development. uce 0395-17 -7- TABLE II EVALUATION OF VINYL CHLORIDE-ETHYLENE COPOLYMERS PHYSICAL PROPERTIES (RIGID FORMULATIONS)* QXOM-7 Blend 3 Tensile Strength/ psi; WC-66-K-I (1) 6880 Tensile Elongation/ % (1) 58 Yield Strength/ psi (1) Room Temperature Stiffness, psi (1) Izod Impact Strength, Ibs/inch/notched; ASTM D 256 (1) 7000 361 x 103 1.00 Heat Distortion Temperature, C; ASTM D 648-56 (1) 77 Melt Characteristics (Plasti-Corder) Apparent Melt Viscosity, Torque, meter grams second-^ 2670 Temperature, C 186 Initial Fluxing Time, seconds Initial Fluxing Temperature, C 330f 174 QYTQ-7 Blend 130 8270 102 7400 408 x 103 0.97 64 2600 186 600 179 (1) Formulation Resin Mark WS 100 parts 3.0 phr Procedure 6" x 13" Roll Mill Mill Temperature Mill Time Press Platen Temperature Press Time 170C 5 minutes 17SC 5 minutes Brabender Plasti-Corder Processing Conditions and Formulation Resin Mark WS* Jacket Temperature Rotor Speed 100 parts 3.0 phr 165C 40 rpm * Mark WS = Barium-cadmium powdered stabilizer available from Argus Chemical Company. ucc 039518 easeco Tamil* Strength, pai; WC-66-K-1 Tamila Elongation, % lorn Temperature Stiffness, *C Irittlanau Temperature, *C Malt Characteristics (Plosti-Confer) Apparent Malt Viscosity, Torque, meter groan ncond * Temperature, *C feitlol Fluxing Tin* Tima, wcomfe Tanparalura, *C Shorn Hatdnan A-2 Oo -8TABLE lit EVALUATION OF VINYL CHLORIDE-ETHYLENE COPOLYMERS PHYSICAL PROPERTYS (FLEXI8LE FORMULATIONS)* 10 phr 20 phr oxoM-r QYTQ-7 QXOM-7 QYTQ-? 6640 159 350 x I03 6540 148 375 x 103 5130 229 80 x !03 5450 217 137 x 103 +42 +42 +12 +18 30 phr QXOM-7 QYTQ-7 3730 4000 275 255 4.5 x 103 8.6 x 103 -6 -2 40 phr___ QXOM-7 6yT*-7 3180 3310 312 302 1.7 x I03 1.9 x 103 -18 -16 50 phr___ QXOM-7 QyTO-7 2640 2820 354 340 0.7 x 103 0.7 x 103 -26 -24 _____ 50 phr QXOM-7 GYf<^7 2280 2390 404 385 0.4 x 103 0.6 x 103 -34 -32 2280 2320 I860 1980 1570 1680 1280 1370 1020 171 175 170 172 161 167 155 158 152 315 1080 110 210 (1) (1) 0) 0) 0) 162 164 155 155 (D 0) (1) (1) (l> - - - - 97 98 90 91 83 Brabander Plorti-Confer Conditions Jockat Temperature 155C Rotor Spaad 40 rpm * Formulatiom, Physical Proparliai and Malt Charoctariitici Resin 100 ports FLEXOL DOP phr os shown Mark M {2) 3.0 phr (1) Immediota fluxing, less than I minute including loading lime. (2) Mark M - Liquid barium-cadmium stabilizer available from Argus Chemical Caipany. 1140 154 0) 0) 86 78 - 8 RESEARCH AND DEVELOPMENT RELATIVE PROCESSIBILITY, FLEXIBLE FORMULATIONS Apparent Melt Viscosity, Torque Initial Fluxing Time Figure 2 1200 Plasticizer Concentration, Phr Plasticizer Concentration, Phr u Apparent Melt Viscosity Temperature Initial Fluxing Temperature ucc 039520 RESEARCH AND DEVELOPMENT PHYSICAL PROPERTIES FLEXIBLE FORMULATIONS Tensile Strength Tensile Elongation Brittleness Temperature Shore Hardness B rittle n e s s Tem perature ucc 039521 RESEARCH AND DEVELOPMENT PHYSICAL PROPERTIES, FLEXIBLE FORMULATIONS Room Temperature Stiffness DISTRIBUTION Mr. A. J. Constanin, 312 Mr. F. D. Dexter, NYO Mr. J. F. Erdmann, 515 Mr. J. H. Field, 515 Mr. C. R. Field, NYO Mr. G. G. Himmler, 312 (5) Mr. J. L. Hockersmith, 515 Mr. D. E. Richardson, 515 Mr. P. T. McCoy, TNY Mr. K. V. McCullough, 312 Mr. J. R. Wilkinson, NYO Dr. N. L. Zutty, 312 Dr. F. E. Bailey, Jr. Mr. D. L. Engle Mr. C. E. Fry Dr. J. E. Glass Mr. R. J. Hanna Dr. R. G. Kelso Dr. R. D. Lundberg Mr. W. R. Manning Dr. C. W. McGary Mr. W. E. Whitehurst Information Retrieval