Document K68Y9KyEMoR0LJRpJ7bM94Q6Q

BUSINESS CONFIDENTIAL PROJECT REPORT received DEC 4 1367 R. N. Wheeler SUSPENSION VINYL RESINSSCALEUP STATUS OF ETHYLENE-MODIF LED DRYBLEND RESINS author: Dean E. Richardson supervisor) Dr. F. E. Bailey, Jr. datEi November 29, 1967 PROJECT NO.i 347 B 10 PILE NO.i 8L02 SUMMARY R. and D. studies showed that the addition of a small amount of ethylene to dryblend PVC resins for calendering and extrusion resulted in a substantial improvement in dryblend time without apparent effect on melt properties. Since this technique yielded dryblend times at least as good as, and in most cases better than any competitive dry blend PVC resin, it was agreed with operating personnel that scaleup runs of rj 50,000 lb. would be made, adding ethylene to four dryblend PVC types: QYTQ-7, QYSC-7, QYSL-7 and QSAN-7. The first three mentioned were for calendering use, while the fourth was intended primarily for wire and cable coating. The ethylene concentration required was approximately 0.5% by the old standard, or 0.9-1.3% hy Dr. Geo. Potter's new Parr bomb standards. The above-mentioned scaleup runs are now complete. Resin pro perties in all cases were approximately as predicted, and the resins sc produced are considered suitable for sampling to selected customers except for the modified QYSC-7, in which case the amount of ethylene added was insufficient. Analyses are shown, along with typical unmodified PVC analyses for comparison. Bearing in mind recent quality control analyses of leading competi tive resins, the data in the tables show that for the first time UCC has proved manufacturing capability to produce a line of dryblend-type resins with dryblend times second to none in the industry. Exploitation of this advantage awaits marketing decisions as to pricing and initial potential customers. INTRODUCTION Earlier R. and D. studies on the so-called "0" resins (vinyl chloride/ethylene copolymers) showed that dryblend times were improved substantially by the ethylene, but that melt viscosities were also affected. Marketing personnel in the Calendering, Flooring and Records Market Area felt that a significant improvement m dryblend times for UCC standard dryblend-type PVC resins must be made to maintain or improve competitive posi tion. R. and D. studies showed that this could be accomplished by the addition of^0.5% ethylene (0.9-1.3% by Dr. Potter's new standards) without significantly affecting melt properties. RESEARCH AND DEVELOPMENT DEPARTMENT CHEMICALS AND PLASTICS UNION CARBIDE CORPORATION TEXAS CITY, TEXAS IJCC 070272 t 2 DISCUSSION The 50,000 lb. scaleup runs for the four ethylene-modified resins mentioned above are discussed in the chronological order in which the scaleups were carried out. QYSL-7 '* This high-viscosity PVC, sold only to Ford, was scaled up first in ethylene-modified form because of an immediate need to counter a competitive resin threat at Ford. Ford has evaluated a sample of Blend B-78, and was so favorably impressed that they have re quested that all future QYSL-7 deliveries be equal to Blend B-78. Marketing and Operating personnel plan to comply. Properties are shown in Table I. Ethylene content could be increased slightly without harming melt properties if further incremental dryblend improvement is needed. QYSC-7 The ethylene-modified QYSC-7 was scaled up in late August, 1967, the resin being collected and packaged as Blend B-83. Unfortun ately, the amount of ethylene introduced was not enough to sig nificantly affect the dryblend times, so while Blend B-83 dryblends faster than typical QYSC-7, it is no better than selected blends of top-quality QYSC-7. Properties of the resin are shown in Table II. No further scaleup efforts are planned for ethylene-modified QYSC-7 unless Marketing can document a specific customer need. QYTQ-7 Ethylene-modified QYTQ-7 was scaled up early in November, 1967. Resin properties are shown in Table III, and were as predicted. It was originally planned to offer this resin for Ford's general purpose business, but price weakness caused a change in these plans. Marketing personnel are considering the best application for offer ing this improved resin. QSAN-7 The ethylene-modified QSAN-7 was scaled up in mid-November, 1967, and was double-washed in the same manner as normal Q3AN-7, in order to obtain good electricals. Properties were as predicted, and Wire and Cable personnel are considering the possibility of offering this resin to the two wire coating firms selected as initial marketing targets. Properties are shown in Table IV. Electrical resistivity can be improved by reducing the sodium bicarbonate in the recipe. CONCLUSIONS 1. The use of small amounts of ethylene in the recipe for dryblend vinyl resins provides UCC a line of products with dryblend performance second to none in the field. Furthermore, melt properties are not significantly affected at this ethylene level. 2. Maximum autoclave pressures generated at the levels men tioned above are low enough that the resins can be made in any of the existing suspension autoclaves at Texas City. 3. Autoclave productivities, in terms of lbs. of resin per reaction hour for the ethylene-modified resins are es sentially the same as for their unmodified counterparts. L. Inasmuch as manufacturing capability for the ethylene- modified resins has been conclusively demonstrated, the burden of the further effort to capitalize on this breakthrough now rests with marketing personnel. `JCC 070273 BIBLIOGRAPHY 1. Memorandum "Production Run of QYSC-7 Resin", J. C. Schlichter to N. A, Gimber, September 15, 1967. 2. Memorandum "Initial Production Run QYSL-7 with Ethylene", W. D. .Bush to N. A. Gimber, November 20, 1967. 5. Memorandum "Scale-Up Run of QYSL-7 With Ethylene", J. C. Schlichter to N. A. Gimber, September 8, 1967. Dean E. Richardson ucc 070274 TABLE I ETHYLENE-MODIFIED Q.YSL-7 Screen Analysis, % through 40 mesh 60 " 80 " 100 " 140 " 200 " Median particle size, microns Heating loss, % Inherent Viscosity Contamination Rating Apparent Density, lb/cf ASTM Plasticizer Sorption, pphr Dryblend time, min./C FORD dryblend time, min./C Dry resin flow, sec. ICMT Fisheyes, 17.5 mil at ^ win. tt ft it ii 10 " " 6 Clear HRP Ethylene, % *** Brabender melt viscosity, ** m-gm./C Blend B-78 Typical QYSL-7* 100 99 76 29 5 1 161 0.4 1.57 2 29 114 7.6/85 15.0/82.5 3.1 90 0 111 1 2 0.41 (0.95) 1820/173 100 1 178 0.4 1.35-1.37 2 31 - 9.8/85 - 2.8 96 0 100 5 2 - 1750-1800/172 * Taken from last 10 blends ** Ford formulation *** value in parentheses is taken from new Parr bomb standards determined by Dr. George Potter. l iaa uOiv 070275 TABLE II ETHYLENE-MODIFIED QY5C-7 4 Screen, $ through 10-mesh 60 " 80 " 100 " llo " 200 " Median particle size, microns Heating loss, <f, Inherent Viscosity Contamination rating Apparent density, lb/cf Dryblend time, min./C Dry resin flow, sec. ICMT Fisheyes, 17.5 mil/lO mil Clear HRP Ethylene, $ *** Brabender melt viscosity, *** m-gm./C Blend B-83 Typical QYSC-7* 100 99 92 60 17 9 158 0.2 1.19 1 50 7.8/85 5.5 103 0/5 2 0.26 (0.60) 1550/167 100 _ 8 116 0.3 1.15 2 31 8.2/85 3.1 99 0/15 2 1500/166 * Taken from last 10 Blends ** Ford formulation *** Figure in parentheses is approximation of Parr Bomb determinations by Dr. George Potter. ucc 070276 * TABLE III ETHYLENE-MODIFIED QYTQ-7 Screen, fi through 40 mesh 60 " 80 " 100 " 140 " 200 " Median particle size, microns Heating loss, Inherent Viscosity Contamination rating Apparent density, lb/cf Dryblend time, min/C Dry resin flow, seconds ICMT Respro fisheyes, 17.5 mil/10 mil Clear HRP Ethylene, % *** Brabender melt viscosity, m-gm/C ** Blend B-330 Typical Q.YTO-7* 100 100 94 62 13 2 138 0.1 0.96 1 32 4.8/85 3.0 110 0/19 2 0.52 (1.25) 1940/155 100 * - 3 137 0.2-0.3 0.96-0.99 1-2 33-34 6.4/85 3.4 102 0/20 2 - 2000-2100/155 Values taken from last 10 production blends ** UCC Method WC-327A *** Figure in parentheses is an approximation by Dr. George Potter's Parr bomb technique. UCC 070277 i > TABLE IV ETHYLEHE-MOT^TFTRTi QSAN-7 -4 Screen, $ through 40 mesh 60 " 80 " 100 " 140 " 200 " Median particle size, microns Heating loss, # Inherent Viscosity Contamination rating Apparent density, lb/cf Dryblend time, min/C Dry resin flow, seconds ICMT Respro fisheyes, 17.5 rnil/lO mil Ethylene, % *** Resistivity, $ of std. Brabender melt viscosity, m-gm/C ** Blend B-lll 100 96 78 49 10 2 151 0.5 1.06 2 55 5.2/82 5.8 111 0/5 0.7 (1.4) 65 1500/161 Typical QSAN 100 - - - 2-5 148 0.2 1.01-1.05 2 55 6.4/84 5.1 106 0/55 70 1510/161 * Taken from last 10 blends ** Ford formulation *** Figure in parentheses is an approximation of results by Dr. George Potter's Itarr bomb technique. UCC 070278 DISTRIBUTION Texas City: Mr. R. M. Arnold Mr. J. H. Barrett Mr. W. D. Bush Mr. R. J. Deluca Mr, J. F. Erdmann Mr. J. H. Field Mr. N. A. Gimber Mr. R. J. Greer Mr. J. L. Hockersmith Mr. F. L. Johnson Mr. K. L. Meisner Mr. A. A. Peterson Mr. L. G. Peyton South Charleston: R. N. Wheeler Technical Center: Dr. F. E. Bailey, Jr. Dr, J. J. Brezinski Dr. J. E. Glass Dr. W. R. Manning Dr. C. W. MeGary Mr. J. J. Smith Information Retrieval Tarrytown * Mr. W. H. Bauer Librarian Bound Brook; Mr. A. J. Costantin Mr. F. A. DeMelio Mr. G. G. Himmler Mr. R. J. Stockman Dr. N. L. Zutty New York Office: Mr. G. P. Bigelow Mr. C. R. Field Mr. J. A. Francis Mr. C. W. Naylor Mr. J. W. Schilling Mr. J, R. Wilkinson ucc 070279