Document bkqB4vLVr8p2zJJ6wvwq7711

""received Or 2 5 1966 ^R. N ^heeler STATUS REPORT EXPLORATORY VINYL RESIN SCREENING PRELIMINARY EVALUATION OF EXPERIMENTAL VINYL CHLORIDE-VINYL ACETATE-ETHYLENE TERPOLYMERS A4mt J. J. Brezinski J. W. Fields Data: January 19 Prafact No.: 399G13 Flla No.: 5U7 SUMMARY The preliminary comparative evaluation in a simple rigid formula of four experimental vinyl chloride-vinyl acetate- ethylene terpolymers prepared at Texas City in pilot-scale facili ties with a sample of VYFS resin indicates the following: (a) The inclusion of ethylene in a vinyl chloride-vinyl acetate copolymer of approximately 85:15 ratio results in a reduction in melt viscosity, lower tensile strength (with accompanying increased elongation) and significant lowering of the heat distortion temperature- (b) Brittleness temperature is essentially unchanged. The relatively significant reduction in heat distortion temperature suggests that ethylene content of these terpolymers will have to be limited for use in rigid applications. Evaluation of additional samples of VYCA, VYCR and experi mental terpolymers and further study will be required to define the quantitative relative effects of inherent viscosity differences and variation in composition on the property changes observed. DISCUSSION Polymer Description The composition of the polymers studied is documented in the following table: ___Resin Vinyl Chloride, % Vinyl Acetate, % Ethylene, % inh QEX-1174 QEX-1175 85.8 86.5 12.8* 12.6* 1.4 0.85 0.539 0.550 QEX-1221 QEX-1222 85.3 85.5 13.7* 14.0* 1.0 0.5 0.530 0.528 VYFS Blend 3125 85.5 14.5 0 0.510 *By difference. Rosoorch and Dovolopmant Dapartmant CtiamicaU Division Union Carbido Corporation uce 039579 2- - The samples were prepared using the Process-10 recipe. Vinyl chloride content was defined using the Paar bomb technique. Ethylene content was defined using infrared techniques, and the absorption curve reference utilized with vinyl chloride-ethylene copolymers. (Whether this represents a good estimate of actual ethylene content has yet to be established.) For the purpose of this report, the analyses are assumed to accurately represent the polymer composition. The samples evaluated differ both in inherent viscosity and composition (Table I). Because of these differences, only generali zed statements relating to the influence of these variables on changes in processing and physical properties can be made from the limited number of samples evaluated. The major purpose of this report is to document the pro perties which will form a base point for comparison as additional evaluations are conducted. Physical Properties The preliminary evaluation of physical properties was limited to a single rigid formulation containing 100 parts resin, 2 phr Dyphos (dibasic lead phosphite), and 1 phr DS207 (dibasic lead stearate). Tensile Strength and Elongation The accumulated teisile data (Table 11) suggest that the inclusion of ethylene results in a reduction in tensile strength and increase in tensile elongation. This phenomenon is observed when the properties of the QEX-1221 and QEX-1222 samples are compared and when the tensile strength of the VYFS sample is compared to that of the experimental resins. The relatively high tensile strength of QEX-1222 sample may be due to the combination of low ethylene content (0.5 per cent) as well as a relatively high inherent viscosity compared to the VYFS sample (0.53 to 0.51). Brittleness Temperature The data shown in Table II suggests that neither molecular weight differences nor the inclusion of ethylene significantly changes the brittleness temperature of the resins studied, though the resin with the highest ethylene content (1.4 per cent) does show a 3C lower reading than the VYFS resin. Heat Distortion Temperature The heat distortion temperature decreases proportionately with increasing amounts of ethylene in the polymer. The data plotted in Figure 1 illustrates the change. This chart suggests that the amount of ethylene included in the terpolymer will have to be limited ucc 039530 -3- in resins intended for rigid applications where there is a critical heat distortion temperature requirement. Thermal Stability The relative thermal stability was assessed using the Copolymer Resin Mill Test (CRMT). The data shown in Table III re veals that the stability of the QEX-1221 and QEX-1222 samples is superior to that of the QEX-1174 and QEX-1175 samples; the stability of the former two resins is judged at least equivalent to that of the VYFS control sample. No reason for the apparent differences in th rmal stability of the experimental resins may be advanced at this time. Conclusions of Physical Property Study The following tentative observations may be drawn from the data: a. Tensile strength is lowered by the inclusion of ethylene. b. Tensile elongation is lowered by both reduction in molecular weight and a decrease in the amount of ethylen in the terpolymers. c. Brittleness temperature is not significantly influenc d by the inclusion of ethylene in the range of compositions studied. d. Heat distortion is the physical property most influenced by the inclusion of ethylene. The heat distortion temp rature decreases proportionately with increasing amounts of ethylene. Processibility The relative processibility of the resins was studied using the C. W. Brabender Plasti-Corder. Two test conditions were used: (A) using a head temperature of 168C and (B) using a head tempera ture of 140C (both at 40 rpm). The formulation is the same as that used to obtain physical properties. The data listed in Table IV permits the following tentative observations: 1. The inclusion of ethylene results in a reduction in the apparent melt viscosity (readily observed in data obtained using Condition "A") as well as in the lower melt viscosity of QEX-1222 vs QEX-1221 as defined for both conditions. 2. The use of the lower head temperatures in the plastograph yields higher melt viscosity and larger over-all differences between samples. The use of the lower head temperature, however, yields data characterized by significantly dif ferent temperatures (152-160C) at equilibrium melt vis cosity which makes interpretation more difficult. ucc 039531 -4- All of the resins (including the VYFS resin) showed im mediate fluxing in the plastograph even when the lower head tempera ture was employed. Additional study of the relative fluxing t mperature of these resins is planned following a procedure suggested by Mr. P. T. McCoy of the Tarrytown Laboratory*: Future Studies Planned The evaluation of additional samples , of VYCA and VYCR, resins of selected inherent viscosity as well as of other vinyl chloride-vinyl acetate-ethylene terpolymers including the QEX-1226 sample is planned. The latter resin (85.5 per cent vinyl chlorid , 1.0 per cent ethylene,7L inh - 0.575) and QEX-1221 resin discuss d in this report have been sampled for evaluation to selected floor ing customers based on an earlier evaluation of QEX-1174 and -1175 in a vinyl asbestos formulation by Mr. McCoy of the Tarrytown Laboratory. The study showed that the terpolymers were more efficient (required lower plasticizer content to yield comparable tile properties) than copolymers of comparable vinyl chloride content and inherent viscosity (1). PERIOD COVERED: LABORATORY ACCOUNT: Attachments: 4 Tables 1 Figure * Unpublished Report, P. T. McCoy (1) McCoy, P. T. and Conkling, A. W., Performance of Vinyl Chloride- Vinyl Acetate-Ethylene Terpolymers in a Typical Vinyl Asbestos Formulation, Memorandum to Mr. E. R. Weidlein, Jr., Research and Development Department, Tarrytown, New York, October 6, 1965. dww ucc 039582 -5- TABLE I GENERAL PROPERTIES OF EXPERIMENTAL VINYL CHLORIDE-VINYL ACETATE-ETHYLENE TERPOLYMERS Resin Designation VYFS QEX-1174 QEX-1175 QEX-1221 QEX-1222 Blend 3125 Poly(vinyl chloride) % (WC-294-A) Ethylene Content,%* Inherent Viscosity (ASTM D-1243 MAthod A) Apparent Density,lb/ft^ ASTM Flow Time, sec/400 cc ASTM Plasticizer Sorption, % Sieve Analysis, P r Cent Through Mesh 40 60 80 100 120 140 200 270 325 Median Particle Size, Microns 85.8 1.4 0.539 36.9 3.2 65 100 99.8 94 87 78 54 25 10 4 103 86.5 0.85 0.550 36.4 3.3 55 99.8 82 65 56 50 41 25 12 7 132 85.3 1.0 0.530 37.8 3.4 58 100 99.5 95 85 72 43 14 5 2 111 85.5 0.5 0.528 40.2 4.0 51 99.8 97.8 92 84 76 59 35 18 10 93 85.5 0 0.510 33.3 5.2 74 99.8 98 93 86 79 67 47 29 17 78 *Infrared Analysis ucc 039583 6- - TABLE II Resin Designation PHYSICAL PROPERTIES QEX-1174 QEX-1175 QEX-1221 QEX-1222 VYFS Blend 3125 Brittleness Temperature (WC-76-A-2) Heat Distortion Tempera ture (ASTM-648-56) Tensile Strength, psi (23-261-19) Tensile Elongation, per cent (23-261-19) Yield Strength, psi (23-261-19) Yield Elongation, per cent (23-261-19) +41C 53C 4670 68 7230 3.0 +44C 55C 4770 67 7100 3.0 +43C 55C 4780 96 6570 2.9 +46C 57C 5120 92 7180 3.0 +44C 63 C 4900 38 7220 3.0 Formulation Resin 100 phr Dyphos (dibasic lead phosphitb) , 2 phr DS 207 (dibasic lead stearate) 1 phr Processing Conditions Roll Mill SurfaceTemperature Milling Time Press Platen Temperature Press Time 155C 5 minutes 160C 5 minutes ucc 039504 -7- TABLE III RELATIVE THERMAL STABILITY (Copolymer Resin Mill Test) Reflectance at 400 Beckman Model B Modified Spectrophotometer Resin QEX-1174 Reflectance Readings QEX-1175 QEX-1221 QEX-1222 VYFS Blend 3125 Milling time, 5 minutes 20 23 38 40 34 10 minutes 7 7 13 15 16 15 minutes 5 5 9 9 6 20 minutes 4 5 8 8 5 CRMT* 27 30 51 65 50 Holding Power, %** 45 43 45 45 45 CRMT = The addition of the 5-minute and 10-minute reflectance r adings. Holding Power is calculated by the following formula: 5-Minute Reading X 4 5 + 10 + 15 + 20-Minute Readings ucc 039585 8- - TABLE IV APPARENT EQUILIBRIUM MELT VISCOSITY (15 Minutes after Peak TorqueC. W. Brabender Plasticorder)* (A) Jacket Temperature 168C; Rotor Speed 40 rpm Sample Size = 59 grams Resin QEX-1174 QEX-1175 QEX-12511 QEX-12512 VYFS, Blend 3125 Apparent Melt Viscosity, Meter-Grams-Sec-1 1000 950 1000 1100 1100 Compound Temperature 167C 168C 168C 169C 167C (B) Jacket Temperature 140C; Rotor Speed 40 rpm QEX-1174 QEX-1175 QEX-1221 QEX-1222 VYFS, Blend 3125 1780 1860 1660 1730 1860 Formulation Resin Djfphos'** DS-207"** 100 phr 2 phr 1 phr 154C 152C 155C 155C 160C '`Under the conditions studied, all compounds yielded immediat fluxing. **Dyphos is dibasic lead phosphite, a powdered stabilizer avail able from the National Lead Company. ***DS-207 is dibasic lead stearate. ucc 039586 RESEARCH AND DEVELOPMENT HEAT DISTORTION TEMPERATURE VS ETHYLENE CONTENT OF VINYL CHLORIDE-VINYL ACETATE-ETHYLENE TERPOLYMERS FIGURE X 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. G. G. Harkreader, 515 Mr. J. C. Hockersmith, 515 I)r. W. R. Manning, 511 Mr. P. T. McCoy, TNY Mr. K. V. McCullough, 312 Mr. D. E. Richardson, 515 Bfr. J. R. Wilkinson, NYO Dr. F. E. Bailey Blr. D. L. Engle Bfr. C. E. Fry Dr. J. E. Glass Mr. R. J. Hanna Dr. R. G. Kelso Mr. W. E. Whitehurst Information Retrieval