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Monsanto Chemicals __ ^.. _ AROCLORS as Co-Plasticisers for Polyvinylchloride Monsanto Technical Bulletin No. P-131 May 1, 1948 Monsanto Chemical Company, St. Louis 4 Mo. SS 4S Selected AROCLORS* (chlorinated biphenyls) used as co plasticizers with tricresyl phosphate, dioctyl phthalate and other plasticizers for polyvinylchloride impart good quali ties to the plastics at a substantial reduction in cost. This bulletin describes the practical use of Aroclors with tricresyl phosphate and dioctyl phthalate in polyvinylchlo ride plastics. In each case the saving in cost of the finished plastics is illustrated. > 39 o n r- o VI > n Registered in U.S. Patent Ofiice IWlirfwmtUn In Rill fcwttoHn l W--4 *n 9m tnpwWnw.itpiMMh 9m Wt li* * to WmmM H b* WIMuli W w* mw! vhm mpowHllly *m ny Uh * moMmI My ovtvlt tow to wm. 0613873 TOWOLDMON0038062 WATER_PCB-00022531 I. INTRODUCTION Under our present economy the selling price of plasticizers such as tricresyl phosphate, dibutyl phthalate and dioctyl phthalate used for polyvinylchloride plastics Are substantially higher than in former years. Aroclors (chlorinated biphenyls), also used as plasticisers for polyvinylchloride, are relatively inexpensive and their use results in substantial savings. Studies of the properties and economies of Aroclor--tric'resyl phosphate mixtures for polyvinylchloride--have been made particularly in France at the Chemical and Electrometallurgies Products Company's Central Laboratory at Salindres. The following data indicates the high efficiency of Aroclors mixed with tricresyl phosphate and dioctyl phthalate as plasticizers for polyvinylchloride and the attractive economies offered by using such mixed plasticizers. II. AROCLOR- TRICRESYL PHOSPHATE MIXTURES COMPARED WITH TRICRESYL PHOSPHATE PREPARATION OF THE PLASTICS The plasticizer mixture was composed of equal parts by weight of Aroclor 1254 and tricresyl phosphate. Polyvinylchloride varying in molecular weight from 45,000; JO,000 to 105,000 atabilized with one percent of lead stearate was used. Conditions for mixing the plastics and working it on the rolls were similar to conditions normally uaed when tricresyl phosphate or dibutyl phthalate, or mixtures of these plasticizers, sre used. The temperature of mixing and rolling the plastics was 140-145C. for 45,000 molecular weight polyvinylchloride and 160C. for 70,000 and 105,000 molecular weight mate. rial. Duration of plastic mixing was 5 to 10 minutes and duration of rolling was 18 minutes. The plastics sheets were molded into teat pieces 130x130x3,1 mm. using a ]pressure of 142 lbs/sq. in* during 13 minutes and then 3,130 lba/sq. in. during 5 minutes of the molding operation. COMPARATIVE EVALUATION OF THE PLASTICS The tensile strength and elongation of the finished plastics are given in the folic>wing compare- tive Table I. TABLE I. Tensile Plasticizer Molecular Strength Elongation Plasticizer Composition Percent Weight Lbs/sq. in. Percent Mixture 50 parts of Aroclor 1254 and 50 parts tricresyl phosphate 105,000 70,000 2,987 2,631 290 300 Tricresyl phosphate 70,000 2,278 1,779 340 300 Mixture 50 parts of Aroclor 1254 and 50 parts tricresyl phosphate Tricresyl phosphate 45 45,000 70,000 45,000 70,000 2,631 3,130 1,991 2,349 265 285 295 305 Mixture 50 parts of Aroclor 1254 and 50 parts tricresyl phosphate Tricresyl phosphate 35 45,000 70,000 45,000 70,000 3,912 4,057 3,060 3,415 120 180 210 230 -2- 0bl3fn<t | TOWOLDMON0038063 WATER_PCB-00022532 These results show that Aroclor 1254 can be used advantageously as a plasticizer for poly vinylchloride provided that tricresyl phosphate is added to it. This is especially true when the plasticizer mixture is used at a level of at least 45 to 50 percent. COST COMPARISONS OF THE PLASTICS In computing costs the specific gravity and current selling price for each material as listed were used. Material Specific Gravity Selling Price Per Pound In Carload Quantity Polyvinylchloride.............................. 1.35....................................$ .33 Tricresyl phosphate.............................1.17.............................................36 Aroclor 1 254 ................................. .... . 1.54 ..........................................1 8 Assuming that the manufacturer desires to make a sheet of the plastics five feet wide, 0.01 feet thick and whatever length can be obtained from 100 pounds of polyvinylchloride, the cost per running foot for each plastics is given in the comparative Table II. TABLE II. Plasticizer ComDosition Tricresyl phosphate Mixture 50 parts Aroclor 1254 and 50 parts tricresyl phosphate Plasticizer Percent 50 Tricresyl phosphate Mixture 50 parts Aroclor 1254 and 50 parts tricresyl phosphate 45 Tricresyl phosphate Mixture 50 parts Aroclor 1254 and 50 parts tricresyl* phosphate 35 Plastics Materials Cost Per Running Ft. for a Sheet 5 Feet Wide and 0,01 Foot Thick t 1.350 1.253 $ 0.097 Savings $ 1.355 1.266 $ 0.089 Savings $ 1.360 1.302 $ 0.058 Savings The results Indicate that the Aroclor-tricresyl phosphate plasticizer combination offers a saving of 10 cents a running foot when 50 percent plasticization is used. At 45 percent plasti cization the saving is about 9 cents and at 35 percent the saving Is about 6 cents a running foot. Use of Increased amounts of Aroclor result in greater savings. 0613875 J TOWOLDMON0038064 WATER_PCB-00022533 III. AROCLOR-TRICRESYL PHOSPHATE MIXTURES COMPARED WITH DIBUTYL PHTHALATETRICRESYL PHOSPHATE MIXTURES Frequently, to accomplish better low temperature flexibility and "'hand" dibutyl phthalate or dlbutyl sebacate plasticizers are added to tricresyl phosphate. The data given in Table 111 shows the effectiveness ol a dibutyl phthalate-tricresyl phosphate mixture as compared with a mixture of Aroclor 1254-tricresyl phosphate based on tensile strength and elongation characteristics. TABLE III. Molecular Weight of the Polyvinyl chloride 70,000 45,000 Plasti cizer Percent 50 40 50 45 40 45 43 40 35 Mixture of Dibutyl Phthalate and Tricresyl Phosphate 23 parts - 77 parts Tensile Elongation Strength Percent Lbs/sq. in. 370 285 2,205 3,556 Mixture of Aroclor 1254 and Tricresyl Phosphate 50 part6 - 50 parts Tensile Elongation Strength Percent Lbs/sq, in. 221 2.987 360 335 300 1,850 2,419 2.987 300 285 240 2,631 3.130 3,558 310 250 225 1,778 2,349 2.848 265 220 170 120 2,631 2,848 3,272 3,911 Comparison of the underlined values in Table III indicates that provided a greater percentage of the Aroclor-tricresyl phosphate mixture is used, it is possible to obtain tensile strength and elongation qualities similar to those offered by using the dibutyl phthalate-tricresyl phosphate plasticizer combination. COST COMPARISON OF THE PLASTICS In the cost computations given in Table IV the current selling price for dlbutyl phthalate at 35.5 cents a pound in carload quantity was used. The specific gravity value used for this plasticizer was 1.046. The table compares the cost of the plastics in terms of running feet for a sheet five feet wide and 0.01 foot thick. The cost comparisons are made against the efficiency of the plasticizer mixtures with reference to tensile strength and elongation qualities of the finished plastics as shown in Table HI. -4- 06l3b7o TOWOLDMON0038065 WATER_PCB-00022534 TABLE IV. Polyvinyl chloride Molecular Weight Plasticizer Composition Plasticizer Percent 105,000 23 Parts dibutyl phthalate and 77 parts tricresyl phosphate 50 Parts Aroclor 1254 and 50 parts tricresyl phosphate 40 50 70,000 23 Parts dibutyl phthalate and 77 parts tricresyl phosphate 50 Parts Aroclor 1254 and 50 parts tricresyl phosphate 40 50 45,000 23 Parts dlbutyl phthalate and 77 parts tricresyl phosphate 50 Parts Aroclor 1254 and 50 parts tricresyl phosphate 35 43 Plastics Materials Cost Per Running Foot for a Sheet 5 Feet Wide and 0.01 Foot ____ Thick $ 1,339 1.252 $ .087 Savings $ 1.339 1.25 2 $ . 087 Savings $ 1.345 1,272 $ . 073 Savings While more Aroclor 1254-tricresyl phosphate mixture was required to give the same plastici zation as accomplished with dlbutyl phthalate-tricresyl phosphate, the cost figures in Table IV show a decided economy In favor of using the Aroclor plasticizer combination. The economic advantage is about 9 cents a running foot of plastics when the plasticizers are used at a level of about 59 percent. At lower plasticizer concentrations this advantage is about 7 cents a running foot, IV. AROCLOR-DIOCTYL PHTHALATE MIXTURE COMPARED WITH DIOCTYL PHTHALATE PLASTICIZER FOR POLYVINYLCH LORIDE In the following Table V the composition and comparative physical properties of polyvinyl chloride plasticized with dioctyl phthalate and a 50-50 mixture of Aroclor 1262 and dloctyl phthalate are given. The formulations are typical wire coating compositions. Each contained 100 parts of polyvinylchloride. The amount and type of stabilizer and clay used in each form ula was identical. -5- 0613877 TOWOLDMON0038066 WATER_PCB-00022535 TABLE V. PROPERTIES OF TYPICAL PVC WIRE COATING COMPOSITIONS Properties Dioctyl Phthalate 50-50 Aroclor 1262 Dioctyl Phthalate Parts Plasticizer/100 Resin Plasticizer, Percent Shore A Hardness Tensile Strength, Lbs/tq. in. Elongation, Percent Modulus of Elasticity at 100 Percent Elongation, Lbs/sq. in. Flex. Temp,, C. % Water Absorption (24 Hrs.) % Extracted Flammability, sec. Volume Resistivity, 50C. % Volatile (24 Hr. 105C.) 50 33.3 82 2710 385 1660 -19 .34 .02 75 5.0 x 1013 4.1 80 44.4 79 247 5 375 1475 -15 0.33 0.05 3 8.8 x 1013 6.8 The composition containing Aroclor 1262 plasticizer is far superior to the similar composi tion plasticized with dioctyl phthalate with reference to resistance to burning. Also, the Aro clor composition offers improved insulation resistance. In other respects the properties of the two compositions appear similar. COST COMPARISON OF THE WIRE COATING COMPOSITIONS The comparative costs of the compositions in terms of a cubic foot of plastics are given in Table VI. The specific gravity value for dioctyl phthalate was taken as 0.980 and the current selling price of 42.5 cents a pound in carload quantities was used. TABLE VI. Plasticizer Composition Dioctyl Phthalate................. 50-50 Aroclor 1262Dioctyl Phthalate................. Percent Plasticizer Plastics Costs Per Cubic Foot $ 1,70 Savings The comparstlve cost figures given in Table VI reflect a saving of $1.70 per cubic foot of plastics or per 100 pounds of polyvinylchloride when the Aroclor-dioctyl phthalate plasticizer mixture is used. 0613878 TOWOLDMON0038067 WATER_PCB-00022536 V. CONCLUSIONS 1. It Is definitely indicated to utilise Arodors (chlorinated biphenyls) as plasticisers for polyvinylchloride provided that tricresyl phosphate or dioctyl phthalate plasticizers are added to it. 2. In using Aroclor combination plasticizers the total plasticizer content of the plastics mate rial will be increased. The use of Aroclors offers attractive savings in the costs of the fin ished plastics materials and results in a substantial saving of tricresyl phosphate, dibutyl phthalate and dioctyl phthalate. 3. In our present economy, and probably for sometime to come, these ester type plasticizers are both short in supply and substantially more expensive than they were in former years, 4. Aroclors are relatively inexpensive and the materials are immediately available in large quantity. When used in the suggested combinations with other plasticizers, the Aroclors are efficient and economical for manufacturing polyvinylchloride plastics materials. The information contained in this bulletin is to our best knowledge true and accurate, but all recommendations or suggestions are made without guarantee, since the conditions of use are beyond our control. Monsanto Chemical Company disclaims any liability incurred in connec tion with the use of these data or suggestions. Furthermore, nothing contained herein shall be construed as a recommendation to use any product in conflict with existing patents covering any material or its use, MONSANTO CHEMICAL COMPANY Saint Louis 4, Missouri New York* Chicago* Boston* Birmingham* Charlotte* Cincinnati. Cleveland Philadelphia* Detroit* Los Angeles* San Francisco* Montreal* Toronto PQB-rh 8M-BD 061379 | TOWOLDMON0038068 WATEFLPCB-00022537