Document x8J6m0Jd4Qwj5M1GygzQ5n2g

*7>, Shell Development Company EMERYVILLE. CALIFORNIA June 22, 1956 TELEPHONE OLYMPIC 3-2 100 Shell Chemical Corporation 50 West 50th Street New York 20, New York PLAINTIFF'S EXHIBIT Attention: Manufacturing Department Gentlemen: l~ "/asiCu trj&rry -------------- -- In answer to your letter of April 9 and your wire of May 8, 1956 we are transmitting our most recent information on the manufac ture and testing of EPON 562 and EPON Adhesive IX. Included is a brief description of the laboratory test procedures and equipment for evaluating EPON 562 in textile applications. We have also included copies of EMS procedures used in analyzing EPON 562. EM3 5MI/5I "Molecular Weight--Ebullioscopic Method" is currently being revised and we will forward a copy of the revised procedure as soon as it is available. If additional copies of these procedures are needed, they can be obtained from the Analytical Standardization Committee. Manufacturing and testing of EPON Adhesive IX is quite similar to that of Adhesive VIII, with which you are familiar. In your wire of May 8 you also requested information on poly(allyl glycidyl ether). Manufacture of this material is in the very early stages of development and we have made only one small pilot batch. A brief description of the procedure used, and the properties of the product, is attached for your information. We are currently reviewing the potential hazards of this process in view of the possibility of further manufacture of PAGE here. Presumably, we will have more experience with this process before you will be required to start manufacture. A description of the glycidyl ether manufacture has been delayed to include the latest information on allyl glycidyl ether. We are currently using a different process which avoids the difficult distillation of allylmonochlorohydrin ether. This work should be com pleted soon and we will send you a description of the process. lam 029005 ABS-013211 Shell Chemical Corporation New York -2- June 22, 1956 We trust that the information on EPON 562 and Adhesive IX will be adequate for your needs in manufacturing these materials in your PDU facilities. If we have omitted any pertinent data, please let us know. vmiT*o R. M. Cole JCR/au Attachments cc without EMS attachment: Shell Chemical, New York: Manufacturing Operations Shell Chemical, New York: Resins and Plastics Shell Chemical, Houston Shell Chemical Union Technical Service Laboratory, New Jersey be: Messrs. C. L. Raymond S. A. Ballard C. R. Nelson M. D. Taylor S. Z. Perry T. F. Bradley W. L. Everson H. W. dejong S. N. Wik J. C. Fspean LAM 029006 ABS-018212 -15- EPON ADHESIVE IX Semi-Scale Manufacturing Practice EPON Adhesive IX is essentially the same formulation as Adhesive VIII except that it contains a dispersed solid catalyst, dicyandiamide. It is particularly suited for long, open-assembly time applications, since it will not readily cure at 300F and temperatures of 545-350F are normally required. Formulation of EPON Adhesive IX is certified under MIL-A-8331 (USAF) and no modification of the amounts of ingredients are permitted. Process Equipment Blending of the adhesives is carried out in a tilting ReadStandard kneader which is equipped with double sigma blades operating at 21 rpm, external heating coils, and a 7.5 hp motor. The unit has a total capacity of I50 gallons and a working capacity of 70 gallons if loaded to 0.9 times the 10-inch bladeradius above the blade centerline. This volume permits the processing ofa full 500-pound drum of EPON resin and allows the kneader blades to break the surface during the entire addition and kneading time. A drum hoist is provided to charge the mixer, which is located at ground level. Finished material is dis charged into suitable containers by tilting the mixer. In addition to the above-described mixer, two other pieces of equipment are utilized in the operation. The first of these is a 100gallon stainless steel tank equpped with heating coil and air-driven propeller agitator. This tank is used for pre-dissolving solid resins (i.e., polyvinyl acetate) in the liquid EPON. The second piece of auxiliary equipment is a Morehouse Hy-R- Speed mill equipped with replaceable carborundum stones with variable clearance. This mill is required for premixing of pigment or catalyst with the resin. Processing The procedure for typical batch runs as carried out in plant equipment is as follows: Formulation EPON 828 Vinylite AYAF Allyl Glycidyl Ether Asbestos Dicyandiamide 100 parts by weight 2 30 8 LAM 029007 ABS-018213 -16- Vinylite AIAF is dissolved in EPON resin by stirring 30 pounds with 380 pounds of EPON 828 for one hour at 160C (320F). The solution is transferred to the Read mixer and blended for two hours at about 70C (3588F) with 150 pounds of asbestos. In a separate vessel 120 pounds of EPON 828 is heated and mixed at 65-70C (149-158F) with 40 pounds of dicyandiamide (Dicy). The mixture is then passed through the Morehouse mill three times using 60-grit carborundum stones with sufficient clearance to keep the temperature below 70C. The EPON-Dicy concentrate is then added to the EPON-Vinylite-asbestos mixture in the Read mixer and the charge completed by the addition of 10 pounds of allyl glycidyl ether. Blending at 70C is continued for one hour to give the finished adhesive. No study has been carried out as to the maximum allowable mixing temperature and all runs to date have been made at temperatures not exceeding 70C. Process Materials EPON 828 and allyl glycidyl ether are supplied by Shell Chemical Corporation. Asbestos 7TF is a product of the Johns-Manville Company and is classified under the designation of "shorts" and "floats". Vinylite AYAF is obtained from Union Carbide and Carbon Corp. The designation AYAF determines the grade and viscosity of this polyvinyl acetate. Dicyandiamide is a micro-pulverized grade supplied by American Cyanamid Company. Titanium Dioxide is marketed under the trade name of Titanox T i-Pure-R and is supplied by E. I. duPont de Nemours and Co., Ltd. Acetamine Orange is also obtained from duPont under the designa tion of GR Cone 175$. Testing Each batch of finished adhesive is tested for tensile shear strength and viscosity. Test specimens are cleaned, assembled, and cured as outlined in Shell Chemical Corporation Technical Bulletins SC:52-46, SC:55-29, SC:55-30> and SC:55-47. They are then tested according to MIL-A-8331, which requires certain minimum performance standards. LAM 029008 ABS-013214 -17Viscosities are run after constant temperature (77F) storage for 48 hours, using a Brookfield Synchro-lectric viscometer with No. 7 Spindle. A maximum viscosity specification of 1 million cp measured at 2 rpm has been imposed upon Adhesive VI. No maximum has been set for Adhesive VIII and IX. LAM 029009 ABS-018215 -18- PREPARATION OF POLY(ALLYL GLYCIDYL ETHER) Following is a description of a single pilot batch prepara tion of poly(allyl glycidyl ether), PAGE. PAGE is made by polymerization of allyl glycidyl ether (AGE) principally through the double bonds. Although this polymerization can be initiated by oxygen and peroxides, di-tert-butyl peroxide is preferred because it allows better control over the reaction and results in a more uniform and reproducible product. Operating Procedures The procedure used in the plant preparation followed very closely that used in the laboratory on 5-gallon scale. The reaction was carried out in a 100-gallon stainless steel Dopp kettle. This kettle was equipped with an overhead condenser and a 12-gallon accumulator. Mixing is provided by dual, counter-agitators, one set of which acts as a wallscraper. The vessel is heated by circu lating hot oil through the jacket and temperature is automatically controlled by bypassing a part of the oil flow through a cooler. Nitrogen is supplied to the autoclave under pressure and the vessel is equipped with a back pressure controller. Following are the steps used in making a batch of PAGE: The autoclave was carefully cleaned free of any materials (acids, bases, heavy metal salts) which might catalyse the condensation of AGE or PAGE. Allyl glycidyl ether from normal plant production was charged (620 lbs.) and the vessel was flushed with nitrogen and pressured to 130 psig. The charge was heated to l8oC, and after checking to be sure that the heat transfer system was working properly, the flow of initiator was started at a rate of 0.1 lb. per minute per 100 lbs. of AGE. Almost immediately the temperature of the oil dropped about 10C indicating that the exothermic reaction had started. Peroxide addition rates were maintained and the temperature was held at l8oC until the desired conversion was reached (22$) as indicated by the required increase in RI. When the last of the initiator had been added, the charge was held at l8oC for 30 minutes to destroy the catalyst and then cooled. Nitrogen pressure was released and unreacted AGE was distilled to a final kettle temperature of l65C at 5 mm Hg. abs. pressure. A nitrogen purge was used to aid in removing traces of AGE. The product was cooled to 30C and drained to drums. LAM 029010 ABS-018216 -19- Yield Charge: AGE DTBP Recovered: AGE Product Conversion AGE to Product 619.6 Lbs. 14.9 472.3a^ 128.3 20.7#w Raw Materials: AGE DTBP 115 Lbs/100 Lbs Resin 11.6 Product Analysis Plant Batch Lab Batch (Typical) Epoxide, Eq/lOOg Ester, Eq/lOOg Hydroxyl, EcVlOOg Acidity, Eq/lOOg Density 20/4 Molecular Weight Viscosity, Brookfield, poise Color, Gardner-Holt 0.724 0.026 0.12 < 0,001 1.1223 424 5.5 9 0.732 0.020 0.13 < 0.001 1.1244 470 6.3 7 Safety Precautions Potential hazards of this preparation are associated with the fact that AGE can polymerize either through the double bond or through the epoxide group with the liberation of a large amount of energy. Furthermore, AGE and probably PAGE decompose exothermally at high tempera tures (250C) giving low molecular weight compounds and causing a rapid increase in pressure under confined conditions. In this pilot batch, provision was made to drop the pressure on the autoclave quickly at the first indication of a run-away reaction. The vessel was also protected by a bursting disc. LAM 029011 a] Some losses were incurred during stripping, which could be avoided. ABS-018217