Document 0qEYJ5x182jgYnryBVoroBvJM

BUSINESS CONFIDENTIAL MONTHLY REPORT TO: FROM: DATE: MEMORANDUM Dr. C. K. Fink Mr. W. H. Bauer May 1, 1968 RECEIVED MAY 10 1968 Wheeler SUBJECT: Vinyl Resin and Plasticizer Summary - Tarrytown Technical Center April, 1968' _________________ CALENDERING, FLOORING & RECORDS VINYL SUSPENSION RESINS FOR CALENDERING (333 S 90) ' 1. VINYL CHLORIDE - ETHYLENE COPOLYMERS a. Vernon Plastics, Haverhill, Mass. With major personnel changes at this account precluding a plant trial on vinyl chloride-ethylene copolymers, all work on this project has been terminated. The data obtained will be applied to the general program detailed below. (W. H. Bauer) b. General Program - "O" Resins1 It was decided at the CF&R meeting at Tarrytown on April 24, 1968 that the program outlined in the November 11, 1967 report will be implemented. Com ments received from the various technology personnel will be incorporated into this study and a new report issued by June 1. Laboratory work will be completed by - November, 1968. This project will be the responsibility of Mr. L. G. Krauskopf. -s,- ` ' '' '*' " (W. H. Bauer) ~'4 2. INTERCHEMICAL CORPORATION, TOLEDO. OHIO ' ,, ' A brief, unscheduled visit to this customer was made to discuss the ' advantages of current production BAKELITE QYSL, Interchemical, now using a high molecular weight Thompson resin in the manufacture of Landau tops, evaluated QYSL - ucc 042142 , U. S3 vr - V-*-? .4C " ` - * 2. two years ago. It failed the heat sealing requirement due to sealing difficulty and blistering. It was felt that the new QYSL would have a better chance at success and was therefore suggested for evaluation. (E. B. Harris) CALENDERING PLASTICIZERS (333 S 50) * 1. THE GENERAL TIRE AND RUBBER COMPANY, TEXT!LEATHER DIVISION, TOLEDO, OHIO A seminar on the use of FLEXOL EPO as a primary, permanent plasticizer and the computer formulating technique was presented to this company on April 18, 1968. As a result, Mr. Halas, the TechnicalDirector, provided three of his current formulations giving us the opportunity to reformulate them using Carbide plasticizers. The work is in progress and suggestions will be made in the near future. (E. B. Harris) .% 2 PHILLIPS FILM COMPANY, AUBURN, PENNSYLVANIA A suggested plasticizer system designed to solve subject's "slip" problem was evaluated by the customer and interest has been indicated. System consisted of 80 per cent DOP and 20 per. cent EX-3 (Escoflex 150). (R. P. Braddicks) " 3. PLASTIC CALENDERING CORPORATION, FARMINGDALE, NEW YORK Due to a revision of commercial standards for vinyl book binders which requires improved low temperature impact resistance, we measured Masland impact on reformulated samples for this customer. Results were submitted in a Technical Service Bulletin., - ." - ' ` . *#,- . "% (L. Krauskopf) "V.- wWV SUSPENSION RESINS FOR FLOORING (333 R 90) 1. SUSPENSION TERPOLYMERS ,. - , , Study of the utility of ethylene-vinyl chloride-vinyl acetate as candidates for vinyl asbestos tile resins has been completed. Results of this are being evaluated in detail. Preliminary interpretation indicates the lower molecular weight version is better than the high molecular weight terpolymer. Plasticizer and , filler requirements are only marginally better than VSJD-10 standard resin. If possible, ucc 042143 4* -- s . *** ^ 3. a lower molecular terpolymer having an inherent viscosity matching VSJD-10 (0.42) should be experimentally produced for additional testing. Light stability of the terpolymers with a conventional stabilizer system is inferior to the control copolymer. Performance properties of these terpolymers would have to be improved prior to their commercialization. (R. P. Braddicks) FLOORING PLASTICIZERS (333 R 50) * 1. UCANE ALKYLATES AS EXTENDERS FOR FLOORING PLASTICIZERS UCANE Alkylates LR, Acid Washed LR and No. 11 were compounded into vinyl asbestos tile as 15% and 20% replacements for primary plasticizer FLEXOL 128. Test results for these stocks and the control using unextended FLEXOL 128 indicated all s tocks containing alkylates were unsatisfactory due to excess volatility and poor mi - gration resistance into asphalt. Modified LR and a sample of HR alkylate will be test d - for this application. /' jk' (R. P.. Bra^dksyVf''^- 2. G721 -FLEXOL 128 BLEND FOR LOW STAININGPLASTISOLS Blends of G721 (ethoxytriglycol benzoate) and FLEXOL 128 were prepared and compared to Texanol AS for plastisol rheology, compound volatility and compound water extraction. Results precluded further interest due to excessively high unaged viscosities as well as high water extractions when compared to Texanol AS. i ? ; : J'% ' ?f" (R. P.Braddicks) 3. FLEXOL 128 SPI volatility tests conducted on vinyl asbestos tile stocks plasticized, with G575, BBP and FLEXOL 128 gave results Which showed BBP and FLEXOL 128 to be ; equivalent while loss for G75 was more than double that of the other systems. These.-^. results provide additional evidence supporting the claim that FLEXOL 128 is a vinyl asbestos tile plasticizer matching the performance properties of BBP. Stocks made - >?S? with FLEXOL 128 also exhibit better colors than BBP stocks of equivalent pigmentations.. ' ' ' `'..-I, :>'*- , (R> P. BraddicksJ' ' '- -- , - ,* *->'. 4^-*' - ^ ';kl\ ' 4. CONGOLEUM-NAIRN. KEARNEY/NEW JERSBY^^^ fca John Humphrey and the writer visited the Kearney Research facilities/,,,, of Congoleum Nairn on April 2, 1968 and met with Messrs. Boba, Friedman, Shalovand Conger. During the visit interest was expressed in low staining plasticizers for UCC"" 4. sheet goods as well as interest in FLEXOL 128 for vinyl asbestos tile. Interest in easy processing resins exhibiting good room temperature physicals was also indicated. Ethy lene-vinyl chloride polymers are being considered as an offering to satisfy this request. (R. P. Braddicks) MOLDING AND EXTRUSION \ VINYL SUSPENSION RESINS FOR MOLDING AND EXTRUSION (211 V 90) 1. BAKE LITE RESIN QSOM-7, BLEND 8 The measurement of processing and performance characteristics of QSOM type resin containing varied levels of comonomer, plasticizer, and filler is nearing completion. This work has been useful in completing one customer service function and will serve in others. 4 . . \ ,, (L. G. Krauskopf) ^^ 2. MACOID INDUSTRIES, DETROIT, MICHIGAN Typical samples and suggested formulas of molded vinyl arm rests based on QSOM-7, Blend 8 are being forwarded to this customer. At the desired hardness (Durometer A = 50-55), it was found that QSQM-7, Blend 8 allowed for no more than a 5% reduction in plasticizer level. This result tends to confirm the prior work for Vernon Plastics which indicated that at high plasticizer concentrations, the effect of the ethylene copolymer is secondary to the effect of external plasticization. (L. G. Krauskopf) 3. BROWN SHOE COMPANY, ST. LOUIS, MISSOURI The development of a vinyl shoe sole composition based on QSOM-7, Blend 8 is dependent upon completion of the measurement of processing characteristics as a function of lubricant level. (L. G. Krauskopf) v PLASTICIZERS FOR MOLDING AND EXTRUSION (211 V 50) 1. GEAUGA PLASTICS CO., CRESTLINE, OHIO ucc W2145 We are still awaiting results of the polystyrene marring tests, which customer had agreed to run on experimental vinyl compositions containing FLEXOL EPO used at primary plasticizer level. ., , (L, G. Krauskopf) 5. PLASTICIZERS FOR WIRE AND CABLE (223 T 50) 1. NEODOL 23 ALCOHOL This alcohol, a mixture of C.o and C.o carbon number alcohols, produced by the Shell Chemical Company, has been evaluated as a replacement for isotridecanol on FLEXOL 13-13 in 90C, UL Class 12 and CSA Class TEW wire insulation. Di (Neodol 23) phlhalate and Di (Neodol 23/isodecyl) phthalate (3:1) each provided better oven aging resistance than FLEXOL 13-13. Insulation resis tances were low, however. If the resistivity of Neodol 23 pbthalates made in pro duction are satisfactory, then the Neodol 23/isodecanol (75/25) alcohol mixture is suggested for replacing isotridecanol. A report has been issued. (E. B. Harris) 2. FLEXOL 1050 The problem of gel formation in this product during storage has not been resolved. Until the cause and cure have been determined, it is suggested that no customer introductions be undertaken. (E. B. Harris) . 3. NARRAGANSETT WIRE COMPANY, PAWTUCKET, RHODE ISLAND This company has been seeking a second source of plasticizers for use in building wire insulation. Their current plasticizer is Santicizer 215. Since attempts at using FLEXOL 63 were unsuccessful because of storage problems, our only alternative was the suggestion of FLEXOL DOP-X. A laboratory program was undertaken to evaluate the result of alternate purchasing of S-215 and FLEXOL DOP- X. FLEXOL DOP-X and equilibrium storage tank mixtures resulting from alternate purchasing did not perform as well as S-215 in TW wire insulation. A report has be n issued. %}.. " ;-V ' ' ` (E. B. Harris) SUSPENSION VINYL RESINS FOR WIRE AND CABLE (223 T 90) 1. QSAN-7 - TYPE I A UCC : W2146 The program for assessment of the dryfolending characteristics , of this resin is complete. As soon as the data have been examined, a report will be issued. w - viCvJsK?, - ,, (E. B. Harris) 6. PLASTtSOLS FOR COATED FABRICS (343 W 15) 1. HEWITT ROBINS, BUFFALO, NEW YORK The evaluation of BAKE LITE vinyl resins and a plasticizer blend of FLEXOL R3M/EPO/TCP for application to this company's conveyor belt coating is near completion. The object is to derive a plasticizer system more resistant to rub-off than the currently used Santicizer 830. , (E. B. Harris) 2. COLUMBUS COATED FABRICS, INC., COLUMBUS, OHIO BAKE LITE QYNV-1 and QYNM-1 were suggested for evaluation by this customer to be used interchangeably with Diamond PVC-71 in their cloth coating operation. These two resins came closest to the control resin (PVC-71 supplied by '..AT. CCF) in the plastisol viscosity test requested by CCF. If these resins are accepted, for plant trial, the next obstacle they must overcome is the CCF mudcracking test i: fji.- This property is evaluated on the production equipment and is one of the reasons we have not been approved in the past. (E. B. Harris) GENERAL PLASTICIZER SYNTHESIS (ALLOCATED) 1. NORBORNANE TRIESTERS In order to extend the series of norbornane triesters previously reported, two new dialkylnorbomene-dicaxboxylates were prepared as precursors for the addition across the double bond. The diesterification of the anhydride function with n-butanol proceeded smoothly and quantitatively, affording a product which was possible to distill. Addition across the double bond with acetic acid and 2 -ethylhexanoic acid afforded di-n-butyl 5-acetoxynorbornene-2, 3 -dicarboxylate and di-n-butyl 5-(l-ethylpentyl) carboxynorbomene-2, 3 -dicarboxylate, respectively.^ The ability to distill the unsaturated compound and thus obtain a pure product should : prove valuble in establishing the structure of these compounds . It has hot beenc^ determined whether the acetoxy adduct is also distillable. A4- Also attempted was the addition of phenylacetic acid to the norbomene diesters of both 2-ethylhexanol and n-butanol. In both cases the acid was recovered^ quantitatively. Thus, it appears that addition of aromatic acid is not practical by this synthetic route. " ' ^ . / ... ucc " ^ 042H7 7. In order to obtain molecules of this structuxe containing aromatic functions, the dibenzyl ester of the norbornene anhydride was prepared. After stripping the excess alcohol, it was possible to distill a product of high boiling point. Upon cooling the compound partially solidified. Assuming this to be the dibenzyl ester, the addition of acetic acid across the double bond will be attempted. Additional quantities of the di-2-ethylhexyl 5-acetoxy triester and the di-2-ethylhexyl 5-(l-ethylpentyl) carboxy compound were also prepared. It is planned to investigate the preparation of these triesters via epoxidation of the double bond, reduction to the hydroxyl compound, and esterification in order to determine whether this approach contains any advantage over that currently being utilized. (S. Solomon) . 2. NEW PLASTICIZERS DERIVED FROM CAPROLACTONE (451 Nil)' A meeting will be held on May 2nd with R&D personnel whose programs lie in the area of caprolactone utilization. After a review of current projects, it is hoped that additional objectives may be set which will maximize use of this intermediate in plasticizers for poly (vinyl chloride) and acrylic-based coatings. End-use applications for consideration include: a. High permanence b. Automotive (non-fogging) c. Automotive (vacuum formed sheet) d. Organosol overlay flooring e. Non-staining plasticizers f. Plastisols g. High temperature wire insulation h. Acrylic lacquers (low volatility) ucc 042148 (W. H. Bauer,' E. B. Harris) 3. CAPROLACTONE - PROPYLENE OXIDE COPOLYMER (451 N 11> -, 1 ^ "'M This molecule, reference 6-HVL-75, a 70/30 weight per cent cbpolyhser was evaluated as a potentially more economical successor to FLEXOL R3M. Permanepc^ studies including volatile loss and water, oil, hexane and soapy water extraction indicate that, although this molecule is a fairly permanent one, it is not as good as FLEXOL R3M . It was deficient in each of the above tests. Unless the performance of this plasticizer can be improved, it is not recommended as a replacement for FLEXOL R3M. (E. B. Harris) 8. 4. GULF NORMAL ALCOHOLS The Gulf Oil Corporation has introduced several new normal alcohol blends which contain approximately 60% linear primary alcohol and 40% 2-methyl branched primary alcohol. A multiple concentration screening has begun to determine whether the phi-ha late ester of the Cy-C9 blend will perform as a linear or branched alcohol. Previous experiences have shown that linear alcohols containing appreciable quantities of branched isomers do not perform as well as pure linear materials. (E. B. Harris) 5. PUBLICATION The Chapter entitled "Plasticizers" intended for publication in the SPE textbook Chemistry and Technology of Poly (Vinyl Chloride) and Related Compositions is completed and will be received from the duplicating department this week (L. G. Krauskopf) ' ' VINYL DRYBLEND GRADE RESIN (333 S 80) The development of test methods for more thorough investigation of parameters which influence the dryblending characteristics of vinyl resins has utilized the Brabender Plasticorder. Initial efforts have been directed toward determining maximum plasticizer take-up at various temperatures. BAKE LITE Resin QSAN-7, Blend 1490 is being compared to Geon 102 EPF1 for purposes of test development, inas much as these two resins have exhibited different dryblending characteristics in wire and cable studies. At this point, a technique for the incremental addition of plasticizer to the sigma head has be are being investigated wi for the two resins,, but ti sideration. f `i W- H. Bauer:bm New York G. P. Bigelow A. E. Donaldson J. T. Ferguson C. R. Field J. A. Francis L. D. Harris J. M. Herbert C. W. Naylor C. E. O'Rourke J. W. Schilling G. C. Shipston J. R. Wilkinson DISTRIBUTION South Charleston F. E. Bailey* J. J. Brezinski (2) J. R. Hazle R. A. Huber R. G. Kelso D. L. MacPeek C. W. McGary E. J. Mills J. J. Smith R. N. Wheeler (Box 8004) W. E. Whitehurst Bound Brook L. M. Baker A. J. Costantin F. A. DeMelio R. E. Gulick G. G. Himmler L. A. McKenna H. ]. Pazlnski F. J- Skiermont R. J. Stockman N. L. Zutty Texas City J. H. Barrett C. E. Bowman M. E. Eisenhour J. H. Field J. W. Fields J. L. Hockersmith D. E. Richardson **'