Document nkB4eYOdKEBO5d4BpEmV3gQE1

e;-;; cegvf? STATE OF MICHIGAN IN THE CIRCUIT COURT FOR THE COUNTY OF MACOMB KENNETH GRIMM, Personal Represetnative of the ESTATE OF HELEN GRIMM, Deceased, , \ 0EC 2 0 1964 vs. Plaintiff, NO. 83-2872 11(> FORD MOTOR COMPANY, a foreign corporation, et al, Defendants. PRETRIAL STATEMENT Plaintiff alleges that defendants, in their industrial endeavors, have contaminated the air with pollutants which caused deceased-plaintiff to incur a carcinoma resulting in her death. Plaintiff has heretofore filed interrogatories, defendants shall answer the same within thirty<(30) days hereof. The parties are going to complete discovery. It is anticipated that at the next pretrial hearing that plaintiff will be in a position to more specifically demonstrate the basis for his cause of action. Adjourn this pretrial to June 19, 1985 at 9:00 a.m. URL U9927 Dateds December 17, 1984 cc: Francis P. Hughes Ralph Valitutti John Lynch Ralph Safford Ralph Barbier Steven Nadeau Dennis M.Haffey STATE OF MICHIGAN IN THE CIRCUIT COURT FOR THE COUNTY OF MACOMB KENNETH GRIMM, Personal Representative of the ESTATE OF HELEN GRIMM, Deceased, Plaintif f, .vs. FORD MOTOR COMPANY, a foreign corporatIon, et a I, Defendants. / Case No. 83-2872 NO Hon. Raymond R. Cashen DEFENDANT STAUFFER CHEMICAL COMPANY'S ANSWERS TO PLAINTIFF'S FIRST SET OF INTERROGATORIES Defendant Stauffer Chemical Company (Stauffer) in answer to Plaintiff's First Set of I interrogator i es ,--sta tes : URL 09928 1. 1963 by American Chemical Company, since acquired by Stauffer. 2. See answer to previous Interrogatory. 3. No. 4. No. 5. a. SCC 676, SCC 676P, SCC 40. b. SCC 676 1973-1976 SCC 676P 1974 SCC 40 1975-1976 c. SCC 676 and SCC 676P are polyvinyl chloride. SCC 40 is a copolymer of vinyl chloride and vinyl acetate. d. 1973: 5,000 IbSH of SCC 676. 1974: 2,797,320 lbs. of SCC t>7 6 and SCC 676P. Information regarding later years is irrelevant due to the fact Plaintiff's Decedent no longer lived in the vicinity of the Ford plant. 6. a. See answer to Interrogatory 5(c). b. See answer to Interrogatory 5(a). c. Stauffer believes that SCC 676 and SCC 676P were used in the calendering process and that SCC 40 was used as an ad- h e s i v e. URL 09929 d. SCC 676 and 676P: Bulk and 50 lb. bags. SCC MO: 50 lb. bags. e. PVC resins are usually processed with other materi als to produce different end products. Stauffer has no specific knowledge of the nature or scope of the processing used by Ford. 7. SCC 676 and SCC 676P: a. April, 1966. b. April, 1966 in Delaware City. c. Don Hunter, now of Tenneco. d. Stauffer sold the Delaware City plant several years ago and is no longer in possession of the described records. To the extent that Stauffer still has records available, these are located in Westport, Connecticut. e. See answer to previous Interrogatory. f. Stauffer objects to the Interrogatory as irrelevant and unduly burdensome and for the further reason that since Mr. Hunter has not been employed by Stauffer since approximately 1971, the requested information is not available. deposition. It can be obtained by SCC 40: a. July, 1969. b. March, 1968 in Delaware City. c. Charles Harrington, whereabouts unknown. d-e. See correspond i ng answers for SCC 676 and SCC 676P above. f. Stauffer objects to the Interrogatory as irrelevant and unduly burdensome and for the further reason that since Mr. Harrington has not been employed by Stauffer since approximately 1971, the requested information is not available. It can be ob tained by deposition. 8. Stauffer objects to the Interrogatory as overbroad, ir relevant and unduly burdensome. 9. Stauffer Chemical Company supplied the warning specified -2- URL 09930 in 29 CFR 1910.1017 to purchasers of its product. 10. No. There was no scientifically recognized basis for recommending a restriction or limitation on the use of PVC products. 11. Yes. a. Not applicable. b. A 500 ppm threshold limit value for VCM was set in 1961 by the American Conference of Government Industrial Hygienists, in 1974, this value was reduced to 200 ppm. OSHA itself adopted this value as the OSHA standard for vinyl chloride which was in effect until April, 1974 when an emergency temporary standard was established, reducing the level to 50 ppm. In late 1 974 , OSHA adopted the present VCM standard for occupational exposure. Stauf fer has complied in full with all applicable federal, state and local safety standards, orders, regulations and laws in connection with the manufacture of its PVC products. No standard has ever been adopted which specifically applies to the PVC resins supplied to Ford Motor Company. 12. Yes. See answer to Interrogatory 11. 13. The PVC products sold to Ford Motor Company were not ma terially changed during the period Plaintiff's Decedent was living on Lafayette Street. Changes made since that time are irrelevant pursuant to MCL 600.2946(3) and are only related to plant process modifications made to satisfy Federal Environmental Protection Agency plant emission requirements. 14. No. 15. No. 16. Yes. a. No. b-c. Not app1icab 1e. 17. Yes. a. Amounts of VCM in PVC generally are unknown. 18. The best answer Stauffer can provide to this technical ques tion is to refer Plaintiff to a paper, "Small Molecule Migra- -3- URL 09931 tion in Products Derived from Classy Polymers", attached to these Answers. Stauffer has no data regarding its products which would provide the information requested. 19. See answer to Interrogatory 18. 20. See answer to Interrogatory 16. 21. Stauffer Product Ford Specification SCC 676 SCC 676P SCC 40 96F51 None 96F181 22. No. 23. No studies have been conducted on volatility since PVC is not volatile. Studies concerning heat stability are irrelevant. Heat stability relates to the usefulness of the product, not its safety. 24. No. a. Stauffer has no duty or right to inspect the opera tions of users of its products. Users of Stauffer's PVC products are sophisticated in the use of those products and are responsible for the implementation of their own safety systems under applicable law and government regulations. b. Not applicab Ie. 25. See answers to previous Interrogatory. 26. a. Stauffer's PVC products were inspected by Stauffer's quality control personnel prior to release for shipment. b. Prior to Stauffer's sale of the plant, the person responsible was Edward Weleski, Quality Control Manager, Delaware City, Del aware. c. To the extent that records are still in Stauffer's possession, they are located in Westport, Connecticut. 27. Yes. foI lowing: Failure to meet standards for one or more of the a. particIe size; b. molecular weight; c . res in color; -4- URL 09932 d. con tamina tion; e. volatiles (water); f. fish eyes (gels). 28. Stauffer has from time to time made changes in manufac turing procedures as a result of rejections which occurred prior to shipment. 29. To the extent that Stauffer is still in possession of these records, they would be in the custody of Tom Tighe, Stauffer Chemical Company, Westport, Connecticut. a. To the extent of Stauffer's knowledge, this answer is not appIicab Ie. 30. Stauffer has no record of ever having engaged in any media advertising of the PVC products in question. 31. Yes. The nature of the materials distributed prior to 1977 is unknown. Copies of representative 1977 materials are at tached . 32. See position papers and other data presented during OSHA hearings in 1974 which are all matters of public record. 33. See answers to Interrogatories 9 and 32. 34. See answer to Interrogatory 6(e). 35. See answers to Interrogatories 18, 19 and 32. 36. See answers to Interrogatories 6(e) and 32. 37. No. PVC products have never been shown to be associated with liver cancer, brain cancer, breast cancer or hematoIymphopoietic system cancer. 38. No, 39. There have been no deaths or cases of liver cancer, brain cancer, breast cancer or hematolymphopoietic system cancer among employees which Stauffer attributes to the inhalation of VCM. 40. No. See answer to Interrogatory 39. 41. With respect to the physical conditions listed in In terrogatory 39, no. 42. a. See answer to Interrogatory 39. -5- URL 09933 b-e. Based upon available records and to the best of Stauffer's knowledge and belief, there are no such cases. 43. Yes. I. a. Plaintiff claimed exposure to polyvinyl chlor- de and other chemicals. b. Court of Common Pleas Cuyahoga County, Ohio Docket No. 976623 Helen Arthur, Executrix v. B. F. Goodrich Chemical Company, et al c. Approximately November 3, 1977. d. Dismissed with prejudice as to Stauffer. e. Not applicab!e. f. See answer to Interrogatory 43(d). II. a. SCC 676, SCC 676P and SCC 40. b. United States District Court Eastern District of Michigan Civi1 Action No. 78 70769 Stanley & Joyce Mjkyska v. Union Carbide Corp., et al c. Apri1 5, 1978 d. None. The claim was settled by the parties. e. Not app1icab 1e. f. Several of the Defendants, including Stauffer, paid a lump sum to the Plaintiffs to settle the claim without any admission of liability by Stauffer or the other Defendants. 44. None at Ford Motor Company, except for a tour by our counsel in April, 1979 as part of another lawsuit. Inspections of other facilities are not relevant to this action. a. See answer to Interrogatory 24. b. Not appIicab Ie. 45. 1965. Delaware City, Delaware. 46. Yes. The monitoring was the result of an inspection by a fire insurance carrier. 47. Air was pumped through a filter and the matter collected was analyzed by gas chromatography for VCM and other substances. At VCM levels above 1 ppm a warning was given and the condition was -6- URL 09934 corrected. If the level exceeded 5 ppm, employees used respirators. 48. Yes. a. A succession of rules since 1974. b. Not appIicab Ie. c. Plant Standard Practice Instructions. Frank Doyle, Delaware City, Delaware. d. See answer to Interrogatory 9. 49 Manufacturing Chemists Association 1825 Connecticut Avenue Washington, D.C. 20009 Organization Resources Counselors 1625 I Street Washington, D.C. 20006 Vinyl Chloride Safety Association (no fixed address) The Society of the Plastics Industry 355 Lexington Avenue New York, New York 10017 American National Standards Institute 1430 Broadway New York, New York 10018 Chemical Specialties Manufacturing Association Washington, D.C. 50 Stauffer employs an epidemiologist at Westport, Connecti cut whose name is Mary Palshaw. 51. August, 1975. a. To organize and direct a department of occupational medicine. b. Westport, Connecticut. c. Organize and institute a corporate medical program with emphasis on industrial hygiene, toxicology and occupational medicine; advise operating divisions of corrective and protective measures in the interest of employee health and safety. d. Wayne C. Jaeschke, Stauffer Chemical Company, West- port, Connecticut. Medical Director: Herbert L. Northrop, M.D., Stauf fer Chemical Company, Westport, Connecticut. 52. 1973. -7- URL 09935 a. Primarily to measure airborne materials in the workpI ace. b. Westport, Connecticut. c. Primarily the measurement of airborne materials in the workpI ace. d. James Call, Westport, Connecticut. Hygienist: John Bolton, no longer with Stauffer. 53. No. There was no scientifically recognized reason for doing so. 54. While it is believed Stauffer may have done so, the in formation requested is privileged, irrelevant and unlikely to. lead to admissible evidence. 55. There has been no such testimony. 56-63. Stauffer will provide the requested information when it becomes avaiIabIe. The answers to these Interrogatories were obtained from Stauffer's records by various Stauffer employees and from answers to similar interrogatories previously provided in Mikyska v. Union Carbide, et ai, Civil Action No. 78 70769, U.S. District Court, Eastern Dis trict of Michigan. In addition, Stauffer employee Herb Northrop provided information for answers to Interrogatories 37 through 42. -8- AFFIDAVIT STATE OF COUNTY OF Connecticut Fairfield ) ) ss. ) ANDREW F. FINK, being first duly sworn, deposes and says that he is an employee of Stauffer Chemical Company, authorized to make this Affidavit and to state that the foregoing Answers to Plaintiff's First Set of Interrogatories are true to the best of Stauffer's knowledge, information and belief. Subscribed and swoa^nn to before me this 11m day of 1984 Andrew F. Fink URL 09936 Ind. Erg. Chem. Prod. Ru. Cev., Vot. 18. No. 4. 1979 a GENERAL ARTICLES Small Molecule Migration in Products Derived from Glassy Polymers WIUIa/n J. Koros' and Harold B. Hopfenberg Department of Chem/caJ Earnerrug. Norm CaroBna State University. Raleigh. North Carolina 27850 ^ Ot-wnJj The Implications of the combined dual mode sorption and partial immobilization transport models on the migration of small molecules from glassy polymers have been considered. Neither dual-mode sorption nor "Immobilization", to'the Sprue used here, contributes to rrg eraible retention of sorbed specie* if the assumption .of local aquFbrii.gr> between the two sorption modes is satisfied. An apparent trapping of otherwise diffusabte species results from the equilibrium partitioning of migrant between polymer and extractant phases rather than from an inherent kinetic limitation to transport The interrelationship between the transport predictions of the partial immobiKzaUon model and the more general concentration-dependent diffusion coefficient phenomenology Is emphasized throughout the analysts. A case study which presents calculated predictions of extraction kinetics of vinyl chiohde monomer from 40-ml poly(vinyi chloride) sheet is dscussed. The analyses pertain to idealized migration of small molecules into foods or more directly to actual extraction protocols for detection of trace components in polymeric materials. The migration of trace amounts of solvents, reaction and degradation byproducts, additives, oligomers, and mono mers from polymeric barriers used in food and beverage packaging can affect consumer acceptance, product quality,and regulatory approval of candidate packaging materials. The serious economic impact related to accurate prediction of long-term migration effects has motivated this presen tation of the thermodynamic and kinetic realities governing transport in and from glassy polymeric barriers. Much of the detailed experimental characterization of the migration of low molecular weight molecules in glassy polymers has focused on C02 transport in support of the massive research and development of polymeric containers for carbonated beverages (Michaels et al, 1963a,b; Vieth and Sbdek. 1965; Toi, 1973; Fenelon. 1974; Kollen, 1975; Koros and Paul, 1978a-c). There is increasing recognition that dual-mode behavior is a rather general characteristic of nonawelling (low concentration) penetrant sorption in glassy polymers (Berens, I974a.b; 1979; Koros et aL, 1977; Barrie et al.. 1978). The migration of trace amounts of solvents, monomers, oligomers, additives, and degradation byproducts should, therefore, be governed by the equilib rium and kinetic implic lions of the dual-mode modeL An unfortunate and somewhat inconsistent designation has been assigned to the Langmuirian component of dual-mode sorption. These species were originally termed "immobile" although the useful transport analyses have also typically assumed local equilibrium between the Langmuirian and Henry's law species. The local equilibrium assumption implies that there can never be a significant difference in the chemical potential of penetrant sorbed in the two modes in any local region of the polymer. This suggests that interchange between species in the two modes is rapid compared to the time scale required for a significant change in the local value of the chemical potential. The validity of the local equilibrium assumption has been verifud by pulsed NMR for ammonia in glassy polystyrene l.-Witik, 1975) iind by numerous transport studies for gases in glassy polymers in concentration ranges corresponding to several thousand parts per million (Fenelon, 1973; Toi, 1973; Koros and Paul, 1978a-c). The confusion regarding the implications of the term "immobilization" on ultimate release kinetics has prompt ed the analysis presented here regarding the effects of Langmuir sorption and "immobilization" on the migration kinetics of trace components from glassy polymers. Al though the "equilibrium criterion" per se is sufficient to permit complete removal of all spedes into an infinite sink, the detailed kinetics of migration are. in fact, affected by the relative populations of Langmuir and Henry's law species and the degree of "immobilization" of the Lang muirian penetrant. The primary objective, therefore, of this paper is the presentation of a detailed and quantitative case study to aid in prediction of migration rates from glassy polymers complicated by multiple sorption modes and various kinetic and equilibrium possibilities. Analysis and Discussion Equilibrium Sorption Isotherms. A variety of equi librium isotherms relating penetrant concentration in a polymer to penetrant concentration in a contiguous fluid phase are observed for polymeric substrates. Gas sorption in rubbery polymers follows Henry's law (Michaels and Bixler, 1961; Stem et al., 1969). Sorption of organic vapors in many rubbers is characterized by an exponential in crease in the concentration plotted as a function of vapor activity (Rogers et al., 1960). Such isotherms are some times referred to as having a BET type III form. More complex behavior involving an inflection is frequently ob served for vapor sorption in glassy polymers over extended concentration intervals. At low concentrations, the concave downward form of such isotherms suggests dual mode sorption effects, while at higher concentrations it ia be lieved that swelling or penetrant clustering effects pre dominate (Borons, 1975; Stannett et al., 1978). The dual mode isotherm, typical of low concentration penetrant C019-7S90/79M21S-03S3S01.00/0 jf 1979 American Chemical Society 1S4 Ind. En). 0*em. Prod. D*v,, VoL 18. No. 4, 1979 U*V MOO( tOIMIOM URL 09938 Figure X. Schematic representation of dual mode sorption isotherm (curve a) comprised of a Henry's law component (curve b) and Langmui/ian component (curve eh sorption in glassy polymers, is presented schematically ia Figure 1. The terminology "dual-mode" derives from the hypoth esis that the concave downward shaped isotherm shown in Figure 1 results from the linear superposition of the individual Henry's law and Langmuir isotherms presented In Figures lb and lc, respectively (Barrer et aL, 1958; Michaels et ah, 1963a,b). The relationship between the total concentration. Cr and the parameters describing the dual-mode sorption isotherm is given by eq 1 Cn'bp C'kr + TTTP <" Thus C a Co + CH (2) where Co is the concentration of penetrant dissolved in the matrix obeying Henry's Lsw (Le., Cq * &qP) and Ch is the concentration of penetrant presumably held In unrelaxed gaps and described by the Langmuir isotherm. The parameter fcD is the Henry's law constant for the dissolved mode and p is the gas partial pressure in the t surrounding bath (alternatively, C* the surrounding bath concentration could be used instead of p). The parameters, Cy and 6 are the Langmuir saturation constant (cm3(STPl/ca*) and the Langmuir affinity constant (atm'1), respectively. The relative contribution of the Langmuir and Henry's law modes to sorption is conveniently ex pressed by the dimensionless parameter X a C^b/k^ Algebraic simplifications in the following treatment are also provided by defining a " b/k& Fickian Transport. The phenomenological transport law describing unidirectional migration of low concentra tions of small molecules in polymeric materials is given by .V = -oj2 (3) where ;V is the observed flux of migrant. Dtg is the effective diffusion coefficient of the migrant, C is the total concen tration of dissolved component, and x is the direction of diffusion. Behavior which conforms to eq 3 is termed Fickian: various concentration dependencies of D,n are often observed and are completely consistent with the definition of Fickian transport (Crank, 1975). The monotonicafly increasing, albeit inflecting dependence of Dttt on C shown in Figure 2 Is characteristic of diffusion coef C, Ind Smi'mI CM*Mratla It, talf<ar Figure 2. Schematic representation of the typical form of the ef fective diffusion coefficient. ** v*. local concentration of penetrant for dual mode tystema ia which the mobilities of component* in the two modes are not equaL ficients for a number of penetrants at relatively low con centrations in glassy polymers (Kotos et aL, 1976; Chan et aL, 1978; Barrie et aL, 1978). According to the dual mode theory, such concentration dependency of the effec tive diffusion coefficient can arise when the mobilities of penetrants in the two molecular environments described by the Henry's law and Langmuir isotherm terms are not equal (Paul and Karos, 1976; Korea et aL, 1976; Koras end Hopfenberg, 1979). Regions of localized lower density (frequently referred to as "holes'^ which are frozen into amorphous polymers as a result of incomplete volume relaxation during quenching of the polymer from the rubbery to the glassy state are presumably the locus of the Langmuirian sorption mode (Barrer et aL, 1958; Michaels et aL. I963a,b; Koros and Paul, 1978a-c), The difEusional mobility of species ia the Langmuirian mode appears to be significantly lower than the corresponding diffcsional mobility of penetrants in the Henry's law mode for most penefranta (Koras et aL, 19T7). The Dual Mobility or Partial Immobilization ModeL The flux resulting from Fickian diffusion of penetrants in the two sorption modes, Co and Ch, can be described by eq 3 using an effective diffusion coefficient or, alterna tively, by eq 4. which recognizes explicitly the possibility of different diffusivities and gradients of penetrant dis solved is the matrix and dispersed in "holes" (Paul and Koros, 1976). Specifically _ *Cu & -Dq"--a--x------ Z?nH---a--x-- (4) where D0 and DH are the constant diffusion coefficients at each temperature associated with diffusion of penetrant sorbed in the Henry's law mode (Co) and in the Langmuir mode (Ch) respectively. Equation 4 is the basis of a gen eralized transport model generally referred to as either the partial immobilization model or the dual mobility modeL Since eq 3 and 4 describe identical fluxes, explicit rela tionships can be derived for D,a in terms of the various dual mode kinetic and equilibrium parameters if the as sumption of local equilibrium (equality of chemical poten tials) of components in the two modes at planes of constant x ia the membrane is made. The resulting expression is given by eq 5 (Paul and Koros, 1976). ]FK a + aCD)* D.a (5) Ix (I +aCD): --I -- I IrxJ. Eng. CTtem Prod. Ros. Dot., Vol. IS. No. 4, 1978 US URL 09939 c,in rtm X Calculated dependence of the ratio of D^/Dp min* dual mode sorption parameters characteristic of VCM in PVC at 30 *C for value* of F " D^JDq between 0 and LQ. The kinetic parameter F = Dh/Dq characterizes the mo bility of species in the Laagmuirian mode relative to species in the Henry's law mode. If F 1.0 (no immobi lization), is a true constant equal to D&. On the other hand, if F a 0 (total immobilization of Langmuirian spec ies, 0) the effective diffusion coefficient can be a strong function of Cq, depending on the values of Ch', b, and ko appearing in eq 5 as K and a. The range of be havior of D^r is shown in Figure 3 for hypothetical cases where K * 5.4 and a 1.5 x iff* ppm'1 for values of F between 0 and 1.0. For the migration of trace additives CD b extremely small and, therefore, eq 5 simplifies to PD(1 + FK) 0*r (1 +JO (6) Under these conditions b effectively a constant arid corresponds to the zero concentration intercepts in Figure 3 for each value of F. Over a significant concentration range, D,g varies con siderably as b demonstrated by eq 5 and Figure 3. It b often useful, therefore, to define a mean diffusion coeffi cient which corresponds to the concentration interval in question. A mean diffusion coefficient, D, b typically defused as (Crank and Park, 1968) Substituting eq 5 into eq 7 and making the common as sumption of local equilibrium between species in the two modes, i.e., C a Cq + C[>JC/(l + aCp) (Vieth and Sladek, 1965; Paul and Koros, 1976), one finds 0=*Dd ]FK (1 + c*Cq1)(1 + aCD|) 1K (1 + aC^ (X + aCD)) (8) The above form of D will be discussed further in the con text of VCM migration from PVC in the following case study. Figure 4. Calculated kinetics for VCM migration from PVC be* tween 30 and 90 *C. Case Study Describing Factors Affecting Migration Temperature. The migration of vinyl chloride mono mer (VCM) in po!y(vinyl chloride) (PVC) has been studied actively since 1974 (Berens, 1974a,b; Berens and Hopfenberg, 1977; Berens. 1979; Haefner and Hughmark, 1978). Berens has measured the temperature dependence of mean diffusion coefficients of VCM in PVC microapheres for concentrations up to several thousand ppm of VCM. The reported values can be used directly over this concentration range to predict the temperature dependence of the mi gration rate of VCM from a PVC sheet of given thickness. These calculations have been performed using graphical solutions for constant diffusion coefficients (Crank, 1975) for diffusion from a 40-mil PVC sheet into an infinite well-stirred bath. The calculated results are presented is Figure 4 over the temperature range from 30 to 90 *C. Since Berens measured mean diffusion coefficients, and the migration calculations were performed within the same concentration interval (0 to 2000 ppm), the mean coeffi cients can be used in the calculations without requiring assumptions regarding the specific nature of the concen tration dependence of 04<r. The highly activated nature of the diffusion process is reflected in Figure 4. In all cases the migration b slow; at 30 *C, it takes more than 50 years to reduce the average concentration in the sheet to a value of less than 1 ppm, while at 90 *C, the corresponding diffusion time is reduced to approximately 1 year. Bath Size. One of the most severe limitations to mi gration can be imposed by the relative volumes of the polymer and the extracting bath. Using values for the distribution coefficient of VCM between PVC and HjO derived from Berens' data (Berens. 1975) migration calcu lations have been performed for various ratios, ff where 0 = VJi- (9) is the bath volume, V? is the polymer volume. 058 tnd. Eng. Chem. Prod. Res. Dev.. Voi. 18. No. 4. 1979 URL 09940 Figure S. Calculated kinetics for VCM migration from PVC at 30 C illustrating finite bath effects on apparent trapping of residual VCM. and K* is the distribution coefficient equal to C/CB. The asymptotic value of X* at low concentrations becomes quite large and K* = 90.1 was used in the calculations here as the most realistic case. Berens has measured a mean diffusion coefficient equal to 2 X 10"13 cm3/s for sorption of VCM in PVC over the concentration interval 0-2000 ppm at 30 C. This mean diffusion coefficient was used with the graphical solutions mentioned above (Crank, 1975) for release kinetics into a well-mixed finite bath. The plots presented in Figure 5 compare residual concentration curves for 0 * 0.1, L0, and infinity. The curve for 0 L0 corresponds to a 22 cm3 sheet of 40 mil thick PVC sus- pended in 2000 cm3 of well-stirred H*0 for the extrapolated distribution coefficient K* * 90.1 under the assumed con ditions. Even for rather large bath-to-polymer volume ratios, apparent trapping of residual penetrant will be observed. Specifically, if a value of 0 100 were used corresponding to immersion of 22 cm3 of 40 mil thick PVC in 53 gal of water, a residual or limiting concentration of 20 ppm would appear to be inextractable from a sheet initially containing 2000 ppm. The ratio of initial to final concentration in the polymer is dependent only upon the parameter 0, and although the kinetics may be affected slightly by extracting over different concentration ranges (e.g., 2000 to 0 ppm, 2000 to 1000 ppm, 2000 to 1S00 ppm, or even 2 to 0 ppm) the residual concentrations can be shown to be approximated reasonably well by curves such aa those in Figure 5 using the constant value of 0 * 2 X 10~lJ cm3/*- The final concentration, C(, divided by the initial concentration, C0, is given by c,/c0 * 1/(1 + 0) (io) Therefore, extraction of 22 cm3 of PVC containing 2 ppm by a S3 gal bath would result in a limiting concentration of 20 ppb in the VCM-containing sheet and a maximum concentration of 0.30 ppb in the water after 60 years. In all cases migration rates are slow and a half-time in excess of 7 years was calculated for the limiting case of the infinite bath. Special Case of the Mean Diffusion Coefficient for Sorption and Desorption. Equation 8 simplifies some what for the case corresponding to integral sorption where D, 0. The corresponding expression for the mean diffusion coefficient for an integral sorption experiment in volving generalized dual-mode sorption and transport in such a case is [gSg] D D0 [1+ U+ ] (U) A corresponding form for desorption when Cp, ** 0 with Co, ^ 0 results from substitution in eq 8. A value of Do (which is by definition concentration independent) can be calculated if a value of F is specified or known for systems conforming to dual mode sorption with measured values of K and a. Berens has demonstrated that a dual mode sorption isotherm describes the low concentration region of VCM/PVC sorption (Berens, 1979). The Berens study provides a value of K s 5.4 and a * 1.5 X 10'3 (ppm*1). Since a value of F had not been measured for this system, the migration kinetics corresponding to the limits F * 1 and F =* 0 have been calculated for equilibrium parameters K =* 5.4 and a 9 1.5 X 10*3 ppm"` and are presented in Figure 6. The values of Dp used in Figure 6 were calcu lated from the measured values of -.<vK, and a re ported by Berens for a total concentration, C, of approxi mately 2000 ppm of VCM using eq 11 with the two as signed values of F (0 and 1.0). The zero concentration limit of D'S was subsequently calculated from eq 6 and used to prepare Figure 6. Once again, infinite bath conditions were assumed and the graphical solution to the diffusion equa tion given by Crank was used to perform the calculations. Although total immobilisation of Langmuirian species significantly retards migration, complete evacuation of penetrant from the polymer is achieved for both limiting .cl> Ind. Eng. Chem. Prod. Rn. Ocv., Vol. 10, Ho. 4, 1979 597 Figure 7. Calculated kinetics for VCM migration from PVC at 30 C illustrating the effects of eliminating the Langmuir capacity (Jf " 0) for the Limiting case of F 0. cases at sufficiently long times. Clearly, the effect of bath volume on release kinetics is much more dramatic than "immobilization" per se. "Zero migration" is not consistent with the assumptions underlying common dual mode' sorption regardless of the degree of "immobilization" of Lasgmuirian species. The effect of the L&ngmuirian sorption mode per se on migration kinetics is explored further in Figure 7. The total immobilization limit (F * 0) has been arbitrarily selected in preparing curve (a) of Figure 7. Clearly, other values of F could be treated as well. The K 0 limit (Henry's law sorption) gives rise to much more rapid desorption than for K> 0 since the mean diffusion coefficient corresponding to eq 11 is equal to Dq if K 0. For all values of K > 0, t> < and desorption is retarded, however total evacuation of the sample is eventually predicted given times which, although noninfinite, are indeed extraordinarily long. Multi-Mode Sorption Involving Relaxation of the Local Equilibrium Criterion between the Various Sorption Modes. If one postulates that an additional sorption mode exists, say "X", corresponding to irrevers ibly bound or "locked-in" sorbate (Gilbert, 1978), then the relationship between C, the concentration of all sorbed species, and the individual components is C = CD + CH + X (12) This postulate becomes a self-fulfilling prophecy in that now the concentration. X, of species originally present in the polymer will persist indefinitely (by definition) re gardless of the extraction conditions. These effects are shown graphically in Figure 8 assuming that a 40-mil PVC sheet containing a total concentration of originally sorbed species of 2.03 ppm desorbs into an infinite sink. The calculations reveal that the results of Figure 7 are obeyed nearly identically, however, the additional component, X = 30 ppb, by definition, remains in the polymer. Mor phological entrapment of trace amounts cf unpolymerized monomer between crystalline regions or within crystal Figure 8. Migration kinetics for VCM extraction from PVC at 30 C illustrating the effects of a hypothetical morphologically entrap ped component, X. The dashed line qualitatively illustrates the protraction of extraction of VCM which would occur if the utunption of local equilibrium is not satisfied. defects has not, however, been demonstrated experimen tally although significant retardation of extraction has been noted (Cope and Comyn, 1979). True equilibrium in the system would only, in principle, be.achieved after the de fects have healed or after impurities have been excluded by slow recrystallization. If the Langmuirian and Henry's law species are not in local equilibrium, an additional retardation will result due to the kinetic limitation retarding equilibration between Henry's law and Langmuirian modes. Completely irre versible sorption would lead to "trapping"; however, any reasonable nonzero rate of transfer between "holes" and matrix would be achieved within some academically long time scale of desorption. These notions have been treated for the case of the total immobilization model (F ** 0) (Tshudy and von Frankenberg, 1973). The dashed plot in Figure 8 qualitatively reflects the direction of the an ticipated effect. Conclusions The migration rates of small molecules from glassy polymers are exceedingly low. In the absence of irrevers ible entrapment or binding of a fraction of the sorbed population, complete evacuation of sorbed species to an infinite bath must occur. The observation of a zero-mi gration rate can result from non-infinite bath conditions, especially for migrant molecules which partition strongly toward the polymeric phase. Moreover, the time-scale of predicted total extraction of species in many realistic cases is of the order of 100 years; therefore, detection limitations can compromise explicit characterization of the&o inordi nately protracted desorption processes. It is, therefore, difficult to separate experimentally truly zero migration from situations corresponding either to finite bath condi- 351 Ird. Eng. Chem. Prog. Pei. Dev, VoL IS, No. 4. 1979 tiona or analytical detection limitations related in part to the staggering values of the predicted extraction times. The wealth of recent literature data in support of the dual-mode model for sorption and transport suggests* however* that the finite bath realities* boundary layer re sistances in the extracting phase, and the time scale of desorption per se* are very likely to be responsible for apparent "zero'* extraction results. Acknowledgment The authors gratefully acknowledge the interest and helpful suggestions offered by Professor V. T. Stannett. This work was supported by the National Science Foun dation through grants ENG 75-22437 and ENG 78-05577. Literature Cited aumc. a. a*j. Potym. Sd., Pofym. f*v%. Ed* 13. iee5 |i97Sk Berrv, A. 14. Banto. 4 A, Slater. J, J. Pafym. Sd* 27. 17? (19S4V Soria, X A_ LArdey. K_ WEarna, U, Am. Own. See. Otr. Cry. Coat. But. . Owen. Prapr* 39. 187 (1978k u Serene, A. A, Pofym. Ptapr* Am. Cham. See* Ot*. Pofym. Cham* 1S(2k 397 (1974a). itorera, A. A, Pofym. Prapr* Am. Own. See* Oh. Pofym. Cham* 19(21, 203 (19740). Banna, A. A, Aeyaw. Uakromd. Own, 47. 97 (197SV JSwana. A. A. hepterarw K. B, ^eeert Owawomam* m Separation Scant*', Vet HI p 300* N.H.UE4, CPC Praaa* Cleveland. Ohio. 1977. ;Parana. A. A, Pofym. Erg. Sct* in pm* (1979k Chait. A. K, Korea. W. X, PeuL 0. A, J. Hirer. Sd* 3. 117 (197k Cop*. A C, Comyn. A. OA Evropaan Sd. Neta*. 6SN-3M. 98 (1979k Crar*. J, "The Usownatic* at Otltunon*. 2nd ad. CWenden Praaa. Oi'orf 1979. Crania. X. Pam. 0* S,, Olttuaon W Pohrmart*. X Crar* and 0. S. Park. Ed-. &*9tar i. Academe Praia. London. 1995. Feneton. P. X. Pofym. np. ScT_ IS. 440 (1973k Ferwon, P. X. in 'Parmaaoery at FkiK F8ma n) CMBnca to Ga*ai. Vsoora and I'dten'. A B. Hootarcaro, Ed- p 2SS. tenure Praia. Saw York. N.T., 1974. Oban. S. 3. Pofym. Pracr* Am. Own. See. Oh. Pe/ym. Own, 19, 845 (1978k Haefrw. A. J, HOgPreaik. S. A, SPE. UATEC Pm* 70 (1979k Koflen, W, *An Evaluation of the 0\aJ Sorption Modal fty (noamemai Detarmnatlon of Transport Parameters". paper praaomad at ho 8001 National lileoQnq of Uw Anwlsan InsBtuw of Owraoi En^sera. Bortorv UA. Sect 9, 1979. Kaos. W. X. PaiX 0- A, Poem. A, J. Pofym. Sd* By*. Ed* 14. 6S7 (1978k Korea. W. X. Pan A. K, PauL 0. A. J. UamOr. Sd.. 2. 189 (1977k Korea. W. X. PsiA 0. A, J. Pofym. Sd* P*y*. fa* II. 1947 (1978a). Korea. W. J, PauL O. A, J. Pofym. Sd* fry*. Ed* IS. 2171 (1978BL Korea. W. X. PaM. Q. A, Am. Own. Sac. Prapr* Oh. On. Coat. f*ur. Own, Sf. 172 (I978ek Korea, W. X. Hopfaooarfl, H. B. Food Tadnot* 33. 88 (1979k Ucmeia, A. $, BiiW. H. J, J. Pofym. Sd.. SO. 393 (198fk LSchaols, A. S, Vletiv, W. A, Same, XL, J. Appt. fryt* 3A, f (1983ak Mcnaeta. A. S, Vletiv W. ft, Bama. XL.;. ActP. fry*.. 34. 13 |i93ok PatX a ft, Keroa. W. X. J. Pofym. Sd* FT**. Ed* 14. 875 (1979k Rogers. C. E_ Slaiwatt. V. T, S*wre, U* J. Pofym. Sd* 45. 81 (1960k SWTWL V. T. Haider. M. L. Korea. W. X. Hferbarp, K B, Am. Own. Sac. Prapr-. Oh. Op. Coat. But. Own, 39. 448 (I9?fk Slam, S. A, MufMkCLU. 7, Qiah. A X. AJChE J* IS* 64 (1989k TeL K, J. Pofym. Sd* fry*. Ed* 11. 1829 (1973k Tfrfr. X A, .ufiaWaasC, J,"Pofym. Sd*fry%. Ed, tt.7327 (1973k vwoi, w. ft, s^tWL lx;, com Sd* 20.1014 (i95k Received for review Just 12,1979 Accepted August 6, 1979 Sperm Whale Oil Replacements from Halogenation of Jojoba Oil Jairrw Wlanlak* and Pnlna Alfandary Oopartmant at Owrtcjf Enginoorin& Dan CLrljn Unhartfly ot the Atopev. ffoar-Shaim. land C 33 o rj Kinetics of the chlorination and bromination of jojoba ol has been studied at different tempermtxxes, sohrenta. and operating eondMona. Chlorination fofiows frst-order kinetics in double bond concentration with an activation energy of -11 kcal/mei Solvents with high tfeiedric constant increase ihe rata of reaction. Bromination riverfves a two-step mechanism with one or two bromine molecules per double bond; up to 0.2 s reaction time the rate is first order In each of the reagents, and afterwards It is first order in the double bonds and second order bn bromcna. Faster rates are obtained lowering the temperatire and/or ina*easing the dfoiectiie content of the sofvent The chlorinated derivative improves the load carrying capacity of the lubricating ofl. The purpose of this work was to study the influence of operating variables on the kinetics of the reaction between jojoba oil and chlorine or bromine. Previous work on the sulfur halogenation of the oil has shown that the straight halogenated derivative may have value as a lubricant ad ditive (Wianiak and Hanoch, 1975, 1978). Jojoba is an evergreen bush of the Btixaceoe family that grows in semi-derirdc areas and yields a nut that contains about 507 of an oft composed mainly of monoesters of the Ca and Ca alcohols and acids, with two double bonds per chain. Details of the economic potential and chemical properties and technology have been recently summarized (National Academy of Sciences* 1977; Wianiak 1977). Jo joba oil and its derivatives have been shown to replace 'sperm whale in all its uses and also, as a source material for new derivatives. Commercial plantation of the shrub is developing at a growing pace and large quantities of oil should be available within ten yean. Halogenated fatty materials find extensi%*e use in the preparation of quaternary compounds, antirotting, flame proofing, and fungicide additives (Sonntag, 1963). Bromi- nated vegetable oils have long been used as a weighting oil in carbonated beverages. The reaction between halogens and organic compounds has been extensively studied, and the literature is well covered by Pouisma (Kochi, 1972) and De La Mare and Bolton (1966). Elementary fluorine normally reacts in a violent manner with olefins and leads to charred products. The other halogens can add to unsaturated compounds by heterolytic processes. The addition of halogens to a double bond features a number of anomalies including high reaction orders, nega tive temperature coefficients, and a strong dependence on the nature of the solvents (De La Mare and Bolton, 1966). Chlorination of olefins in nonpolar media bos been ex plained by ionic and free-radical reaction mechanisms (Poutsma, 1935); strong evidence indicates the possibility of a radical mechanism in the case of brominaticn (Serguchev and Sergeev, 1972). According to Banaford and Tipper (1973), the rate of addition to a double bond is increased by the proximity of an electron donor group and decreased by an electron- 0019*7890/79/1215-0358S31.00/0 0 1979 America* OefricaJ Society ( URL 09943 SAFE OPERATING FflrcSPrRKS INDEX Chemical Plant Title Latest Issue Date Wona High Pressure Water Cleaning Unit 7/70 Cleaning of Strainer Under Drop Valve on Plastisol Charge Vessels Reactors #45, #46, #60, and #70 4/70 Use of Emergency Wrenches in Chemical Plant Reactor Rooms 3/70 Tank Car Record 9/69 Vessel Cleaning 9/69 Power Failures * Location of the 8 Chemical Plant Gas Alarm Push Buttons and Their Signals 8/69 5/69 Power Failures 3/69 Emergency Mill Instructions 3/69 Colored Cards 2/69 Operators Use of Colored Cards 2/69 Reactor Operators Building #1 Duties When Fire Call Signals 1/69 Bad Cas Leaks Occur 11/66 Flushing Reactors Fire Call Box Locations 9/66 Stopper Addition to Reactors During Power Failures 6/68 Protective Equipment 8/6? Replacing Reactor Seals 7/65 Loading and Unloading Trailers 8/64 Reactor Pressure Testing 3/64 Reactor Post-Charge X 3). -- imt t-1*-- /-* d 4 jy* A ^4 -- i. !SZ:~ /--'a*'- Cl-~ -"`5 3/64 y/7/ Chemical Plant Page 2 Title * Latest Issue Date Charging Reactor 3/64 Pre-Charging Reactor 3/64 Operators of Propane or Liquefied Petroleum Tractors 11/63 Operators of Gasoline and Electric Trucks, Tractors and Transveyors Resin Plant Fire Call Boxes 10/70 ccs Mr* F. F. Hoy SAFETY DE PARTMEtfT URL 09944 URL 09945 GENERAL SAFETY RULES FOR ALL EMPLOYEES The, following rules hare been drawn up for your protection and must be observed: 1. Keep your mind on the job at all times and give your work your entire attention. 2. If you feel ill or in suc-h condition as to interfere with your work, report at once to your Supervisor or Foreman. 3. Cleanliness is a must. Do not allow oil, grease or other refuse to gather on machines or floor* Good housekeeping must be observed at all times. V. All cuts and bruises should be-treated at the plant Dispensary. Be sure to notify your Supervisor or Foreman if you cut or bruise yourself. 5. KHorserlay" will not be tolerated. .6. DO NOT REMOVE ANOIKER' PERSON1S RED TAG FROK EQUIPMENT OR v MACHINERY OR START -WITHOUT PROPER AUTHORIZATION W.EN TAGGED U I 7. Employees are encouraged to wear safety shoes at all times. 8. Safety glasses or other appropriate eye protection should be worn when needed. 9. Chrsck your equipment daily and promptly raport any unsafe conditions to your Foreman or Supervisor* 10. Shew the proper respect for other employees. Be concerned with their safety as well as yours. 11. Gambling and/or*tne use of intoxicants will not be permitted. 12. Smoking is permitted only in areas designated as such. 13. Care should be taken when using compressed air. Do not point nozzle at yourself or any other person. Never use compressed air to blow dust from your clothing or hair. 14. No wrist watches, rings or loose clothing should be worn. 15. Care should be used when coving hastily throughout your own area or the plant proper. Refrain from running. 16. Employees are required to learn the specific safety procedure which applies to the job assignment. 17. Know the proper handling of chemicals, solvents, flammables. ot other hazardous materials. Check with your supervisor tf 30U are net certain. SAFETY DEPARTMENT 2/63 CERTIFICATE OF SERVICE The undersigned hereby certifies that he caused a copy of the foregoing Answers of Defendant Firestone Tire & Rubber Company to Plaintiffs* First Set of Interrogatories to be served on all defense counsel of record by United States Mail, this 25th day of April, 1980, as follows: URL 09946 Robert A. Marsac, Esq. Dykhouse & Wise 11th Floor Buhl Bldg. Detroit, Michigan 48226 Ralph F. Valitutti, Esq. Kitch & Suhreinrich, P.C. 2030 Buhl Bldg. Detroit, Michigan 48226 Ralph R. Safford and George H. Meyer, Meyer and Kirk 100 W. Long Lake Road - Suite 122 Bloomfield Hills, Michigan 48013 Esqs. Frank K. Zinn, Esq. Dykema,Gossett,Spencer,Goodnow & Trigg 35th Floor, 400 Renaissance Center Detroit, Michigan 48243 Gerald G. White, Esq. Pattersons Patterson, Whitfield,Manikof & White 10 West Square Lake Road Bloomfield Hills, Michigan 48013 B. I. Stanczyk, Esq. Plunkett,Cooney,Rutt,Watters,Stanczyk & Pedersen 1000 Guardian Building Detroit, Michigan 48226 Richard A. Harvey, Esq. Harvey,Kruse & Westen, P.C. 1590 First National Building Detroit, Michigan 48226 Richard J. Tonkin, Esq. Vandeveer,Garzia,Tonkin,Kerr & Heaphy, P.C. 3250 Guardian Building Detroit, Michigan 48226 o Stauffer Chemical Company ;' ' PIASJICS DIVISIQN' Sa's Offil-s: V.'csiport Co^nectic-`-T'.-:r-^hcr,e (203) 222-3CCO ./' P<ocj'_ic`s latcrd'cry; P.O. 3c* ~e'd .`.rte CilDETT&'<phene (bcV) S34-7i?5 O' :-40r. . . ; ''V V;^ F VC COPOLYMER DISPERSION ESiPstl ~ _ : . ' r vS SCC-40 is a vinyl chloride*-vinyi acetcte copolymer plastisoi dispersion, resin 'with lo.v paste viscosities, excellent heat stability .hd repid fusion characteristics. SCCMO has been successfully .used in mecha/v '" ic3ffy` frothid foam, solid rug backing, faminct/ng' fabric coating, . flocking adhesives and many other applications. - V .' -= ; .C r---_ _ ''i'-'N, . TYPIOVL RcSIN/PROPERTieSr O;v/u'r;>.'ivvX ' ASTM Classification ' Appsarancs: Relative Viscosity ::V ._ f AStM D-1755-66' - .0-334 ;;Visual ; ^v`V* V.' White Powder cyclohexanone, 25C V.-'ACTKl n'l'lAV I'A 1 l 2.35 1,04 ' > 0.4% v: * 14 lbydi. fi. 1.6% : 1.39 V v 4J8*V^ i ' ______ ______________ _ ^ V. - Brookfield2 rwn'*8aged2hrs,;l aged 2 hrs.-. ' Air .Released SCCQ-15* Height of Rise %, Increase TYPiCACfUSEO'fTum'1, PROPERTIES?; : Heat Stability'. Tensile Strength Ultimate Elongation 100% Modulus ' ASTM D-1003 . *-. 35QrP*oven aging, initial discoloration - ASTM D-832. : r ASTM 0-882 . J*:. ASTM D-832- . - r 65 poise' .60 poise 221_ppfse'i:' ..24$'poise i'-;'; '187 poise Tv 50 microns" * KS*F sco% d X) VoD 13% 20 min. 3000 p$i 500% 850 psi o : r 7 cres:- 1. S03 3-n. resin and 330 gm. OOP, Hcbart N-50 rrised 5'nin. No. 1 speed and '0 min. -e No. 2 speed, urdese^tca. 2. 20 miis/containing 60 pnr. POP and 2 pnr, Vark 29. desired sol. fused 5 rr.in. "v F on Ferro P'-ne. VALUES ??ZZZ\TETO APE ;* iCAL AND INTENDED TO SERVE AS GU'CES ONLY 1 To tTe L--S5 of C'_r ! jf a c`.~z T-.ns z~.`r c n-<:: r | N\':K-:ng re^c n .va.-.-j i c * ' .`n-s-d ,'si j-p. - | ,n corf, -t /.i:r> c.;=.i<- j Liter;;.? :r- .-.-c rr :? . ' 5 .. i - 1 ' N.. VI . ^I MU i72 4"T >. lT>. 1 4"MT rI rk ?I i./ .A-A IU> r** T A ir,11 4/ 'v!, <s0t: - , ii ,-- : t. \ V 5STPORT, CONNECTICUT 06330 roo: >2 >-::oo Stauffer Chemical Company FUSTICS DIVISION Sales Office: Westport Conneclieutflefephone (203) 222-3000 Products Laboratory: P.O. 80* 320, Delaware City, DE/Telephone (302) 834-7458 o SCC-Q7Q PVC HOMOPOLYMER SCC-676 is .a medium molecular weight PVC homopolymer, suitable *;*>* V- . for both' rigidand, flexible applications.^ SCC-676 is exceptionally low in gels and . finds, wide, acceptance'In calendered . film and **." sheeting.'Also SCC-676.because of its low fines level is suitable; -Afor rigid dry' blends where, buik handling requires good dry flow. f . " ~ -.'.A /: .V,?-,--'.3??? ;'A " . i , - - ; v* ** * Suggested Applications:. SCC-676 is' useful in both flexible . t*.-i.i.,i .* s' ASTM Classification: ? RelatIve>iscosity.:v - >' Inherentviscosity A Volatiles < r? 'C' - Apparent Density?- r,; - ' ' Sieve Analysis. - 0 'VH-.; ASTM 0-1.755 ' *" *.. in Cyclohexanone, 25 C ' ASTM D-1243(A) A' ' . SCC 02, 15 min. @ 105 C ASTM 0-1895 V' ASTM 0-1921(8). ... Retain on 40 mesh Retain'on 100 mesh Retain on 200 mesh C 30 r-- uoo C-UJD CO GP4-15453 T2.24 .95; 0.25% 0.50 gms/ml. none 40% 95% To the best of o'er knowledge, the information preserved here is true and accurate. Since 3 VALUES PRESENTED ARE TYPICAL AND INTENOED TO the conditions under whicu our materials are used are b?>ond our control, all suggestions and recommendations are made without guarantee. Staffer cal Company hereby disclaims any liability incurred in connection .-.ith the uses of these caia or suggestions. SERVE AS GUIDES ONLY Nothing herein contained should be construed as a recomrr.encat^cn to use any product in conflict with existing patents covering any material or its use. STAUFFER CHEMICAL COMPANY PLASTICS DIVISION WESTPORT. CONNECTICUT 0 6 8 8 0 (203)222-3000 STATE OF Ml CHI CAN IN THE CIRCUIT COURT FOR THE COUNTY OF MACOMB KENNETH GRIMM, Personal Representative of the ESTATE OF HELEN GRIMM, Deceased, PI aintiff, vs. FORD MOTOR COMPANY, a foreign corporatIon, et a I, Defendants. / Case No. 83-2872 NO Hon. Raymond R. Cashen PROOF OF SERVICE STATE OF MICHIGAN) ) ss. COUNTY OF OAKLAND) Kathleen Wilson, being duly sworn, deposes and says that on the 18th day of December, 1984, she erved copies of Defendant Stauffer Chemical Company's Answers o Plaintiff's First Set of 1nterrogatories and Proof of Service upon: URL 09949 Mr. Francis P. Hughes Bebout, Potere, Cox $ Hughes, P.C. 1 000 W. University Drive, Ste. 314 Rochester, Michigan 48063 Mr. Dennis M. Haffey Dykema, Gossett, Spencer, Goodnow 6 Trigg 35th Floor 400 Renaissance Center Detroit, Michigan 48243 Mr. Steven C. Nadeau Dickinson, Wright, Moon, Van Dusen 6 Freeman 800 First National Building Detroit, Michigan 48226 Mr. John J. Lynch, III Vandeveer, Garzia, Tonkin, Kerr, Heaphy, Moore, Sills and Poling, P.C. 155"0 N. Woodward Avenue Birmingham, Ml 48011 Mr. Ralph W. Barbier, Jr. Barbier, Coulet S Petersmarck, 34820 Harper Avenue Mount Clemens, Michigan 48043 P.C. Mr. Ralph F. Valitutti, Jr. Kitch, Suhrheinrich, Saurbier 6 Drutchas, P.C. 2000 Buhl Building Detroit, Michigan 4J226 by placing the documents in fully addressed, stamped envelopes and by depositing the envelopes in a United States Mail Receptacle. Subscribed and sworn to before me this 18th day o / December, 1984. r PaTr i c!T"KT_Ro3e , Rotary FuETTc Oakfand County, Michigan My commission expires: 1/9/88 , 't 1 *./. n<>V*/_/__ '// /v2 Rath Ieen WiI son