Document 4aaXnmVd8Z0w364bJwDn6kXwp

I-IM (MM) inter-office memo TEHNEGO CHEMICALS, INC. OCT 2 0 1370 to Route List from e. Farber SuBJECT Vinyl Acetate Monomer AT AT Flemington date October 19, 1970 copy to H. B. Carr E. J. Hourihan M. W. Williams In addition to the tests now proceeding (e.g., LOP 855-1) to ascertain the usefulness of U.S.I.'s monomer, the attached notes from Leonard's article on VAM which appeared in High Polymers 2k, (l)j 265 (1970) and the Borden test procedures may also serve a's* guidelines for possible comparisons and evaluations of YAM. EF:df Att. COLORITE 006038 TTHE "BORDEN DILATOMETER TEST"-FOR REACTIVITY OF-VINYL ACETATE MONOMER The use of dilatometry to study polymerization kinetics has been used in scientific researches for some time. This method has now been adapted by the Borden Chemical Company to give a very sensitive laboratory test for monomer purity. Its outstanding advantages are that it provides quantitative polymerization rates and induction periods in a very short time with a few milliliters of sample and a simple apparatus. This data, in addition to indicating whether the monomer poly merizes at a normal or abnormal rate, also provides specific information as to whether such abnormalities are caused by the presence of polymerization "inhibitors" and/or "retarders." Excellent correlation has been established between such testdata and large scale polymerizations. TEST METHOD Apparatus: 1. Constant temperature bath (50^ 0.1C test temperature). Bath liquid level should be high enough to cover top of dilatometer. 2. Dilatometer (See figure 1) The Dilatometer stem is constructed of 2 mm. I.D. precision bore pyrex glass capillary tubing 230 mm. in length. The capillary stem is graduated in mms. with every 5th mm. mark being longer for ease of reading (precision bore capillary tubing may be purchased from Kontes Glass Co., Vineland, N. J.) and every 10th mark (1 cm.) being numbered. The numbering starts with zero at the top and increases downward. A graduated stem length of 200 mms. out of the 230 mm. total length has been found to be satisfactory. The spherical bulb at the bottom of the stem is about 10-12 ml. in volume. The vapor jacket surrounding the top of the dilatometei is made of 10 mm. I.D. pyrex glass tubing and is attached to the stem with a piece of rubber tubing, (Details of fabrication may be obtained from the Borden Chemical Co., Geismar, La.) 3. Hypodermic syringe equipped with 12 inch long metal needle of such diameter that it can be inserted into the 2 mm. I.D. stem. Alternatively, a piece of Teflon or other tubing may be used in place of the 12 inch metal needle. 4. Stoppered weigh flasks or Erlenmeyer flasks. 5. Time piece capable of being read in minute intervals. Materials: 1. Benzoyl peroxide recrystallized. (See procedure at end of this article) 2. Vinyl acetate monomers. These re<ammcndotion* end suggestions for l!. o*e of our moteriafi ore based on our best experience and knowledge, but we do not guarantee the results la be obtained in customer's processes. Prices subject to change without notice. THE BORDEN CHEMICAL COMPANY A Division of The Borden Company MADISON AVFN11F NPW YHPK N Y 10M7 - TeUnhnnp* Aron Prtrl** 01? MDrrnv Hill COLORITE 006039 The Borden Dilatometer Test for vinyl acetate monomer has already been presented as a means of measuring quantitatively the reactivity of a given monomer. The gas chromatograph provides a very sensitive instrument for characterizing the nature and amount of impurities present in a given mono mer. A combination of the dilatometric and gas chromatographic data provides an excellent measure of the quality of a given monomer. The Borden Chemical Company uses both of these analytical techniques (in addition to other more standard analyses) for continuous routine quality control test ing, in order to insure the highest product quality and uniformity. Figure 3 shows a comparison between the gas chromatograph for Borden's commercial vinyl acetate and those of three other commercial producers. These chromatographs were run one immediately following the other with the identical instrument settings. Impurities numbered as 1, 2 and 3 have not been positively identified as yet. The outstanding purity of Borden's monomer is evident from the fewer number of peaks and by the much lower peak heights (and areas under these peaks). Analysis Data Instrument: Column Packing: Column Length: Column Temp.: Carrier Gas: Sample Size: Beckman GC-2A (TC and HF detection in series) 50:50 Pluronic P84 - Fatty acid ester, 35% on Chromosorb P Support 8 feet, 1/4 inch diameter aluminum 120C, isothermal Helium 30 psi inlet 5 microliter Hydrogen Flame Detector Hydrogen: 3.9 psi Oxygen: 5.0 psi Sensitivity: 5 x 101 attenuation Recorder: Fisher 1 M.V. full scale deflection Chart Speed: 1 inch/Min. < ThM recommendation* ond tugguitluns for tha in* of our natarioli oro boiod on our brit ojtporfonco ond litswlrd^i, inf wo do not guaront** thn rtiulti fo b* obtained In cuitomor'i proceiui. Pricoi ivb]t fa cbcngo without notkn. THE BORDEN CHENICSL CQ/V3PANY A Division of The Borden Company 350 MADISON AVENUE, NEW Y0.7K 17, N. Y. - Tolophono; f.VJrray Hill 7-41 CO -_t-t. ijj.. COLORITE 006040 HONOMERS >ducers of vinyl acetate monomer ble '8). It is, of course, important id that monomer produced in the ve somewhat different properties. analysis !% minimum 10% maximum 05% maximum 4% maximum tortess to light yellow .3-73.0'C >335-0.9340 >-17 ppm 15-325 ppm JO-165 min 99.9% 0.005 % 0.002% 0.02% Colorless 72.3-72.9C 0.9336 15 ppm 300 ppm 140 min none i f America (46) 0.010 wt % maximum 99.9 wt % minimum 0.005 wt % maximum 0.04 wt % maximum 72,5-73,0'C 0.9335-0.9340 5 maximum 130-150 min critical Company (43) 99.S% minimum 0.015% maximum 0.007% maximum 0.04% maximum 0.9335-0.9345 5 maximum 72.3-93.0 12-15* ' None 130-165 0210 minimum 220 maximum VINYL ACETATE TABLE 8 (continued) 285 D. Monsanto Chemical Company (48a) Form Color Assay Aldehydes Acidity Water Nonvolatile matter Distillation range Specific gravity (a, 20/20 C Inhibitor Clear liquid free from suspended matter 5 maximum (APHA platinum-cobalt scale) 99.8% minimum 0.013% maximum (calculated as acetalde hyde) 0.007% maximum (calculated as acetic acid) 0.04% maximum 0.015% maximum 72.3-73.0'C at 760 mm 0.9335-0.9345 14-17 ppm hydroquinone Shipments with longer activity time can be patterned to customer requirements. * Available with 3 5 ppm hydroquinone on request. ' Borden reactivity test by dilatometer. IV. ANALYSIS Gas-liquid chromatography is an excellent tool for determining the nature and amount of impurities present in monomer samples, A technical data bulletin (43) of one of the manufacturers gives detailed information on the instrument involved, column packing, sample size, and sensitivity of the method. The Borden Chemical Company (43) has introduced the "Borden Activity Test" as a means of specifying the reactivity of vinyl acetate in polymerization. This dilatometric method provides information on the nature of impurities which influence polymerization rate, differentiating between those which are polymerization inhibitors and those which arc retarders. Figure 4 shows data obtained from polymerization of vinyl acetate at 50C using 0 5% benzoyl peroxide as initiator. This information leads to determination of induction time (here 193 min) and initial rate of polymerization (here 0.24%/min). It has been stated that a high-purity commercial monomer inhibited at the 15 ppm hydroquinone level shows an initial polymerization rate of 0.20-0.24 %/min and that, again at 15 ppm I hydroquinone, induction times are normally 180-200 min. Lower rates than I 0.20%/min indicate the presence of polymerization retarders. Higher induction times than 200 min indicate the presence of an inhibitory impurity. Acetaldehyde as an impurity in vinyl acetate is determined by adding a sample of the monomer to excess IV sodium bisulfite solution. The unj reacted bisulfite is back-titrated with 0.1 Ar iodine solution using starch i as indicator, t IIi i COLORITE 006041