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Monsanto Tectinical Bulletin No. P-131
May 1, 1946
Monsanto Chemical Company, St. Louis 4 Mo.
A R O C L O R S As Co-Plasticizers for Polyvinylchloride
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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 Arodors with tricresyl phosphate and dioctyl phthalate in polyvinylchlo ride plastics.
In each case the saving in cost of the finished plastics is
illustrated.
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Registered in U.S. Patent Office
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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 plasticizers for polyvinylchloride, are relatively inexpensive and their use results in substantial savings.-
Studies of the properties and economics of Aroclor--tricresyl phosphate mixtures for poly-
vinylchloride--havc been made pafticularly in France at the Chemical and Electrometallurgies
Products Company's Central Laboratory at Salindres.
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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 plasticizer s.
II. AROCLOR- TRICRESYL PHOSPHATE MIXTURES COMPARED WITH TRICRESYL PHOSPHATE
PREPARATION OF THE PLASTICS
The plasticizer mixture w&s composed of equal parts by weight of Aroclor 1254 and tricresyl phosphate. Polyvinylchloride varying in molecular weight from 45,000; 70,000 to 105,000
stabilized with one percent of lead stearate was used.
.
Conditions for mixing the plastics and working it on the rolls were similar to conditions normally used when tricresyl phosphate or dibutyl phthalate, or mixtures of these plasticizers, are 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 test pieces 130x130x3.1 mm. using a pressure of 142
Ibs/sq. in. during 13 minutes and then 3,130 lbs/sq. in. during 5 minutes of the molding
operation.
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COMPARATIVE EVALUATION OF THE PLASTICS
The tensile strength and elongation of the finished plastics are given in the following compara
tive Table I.
TABLE I.
Tensile
Plasticizer Composition
Plasticizer Percent
Molecular Weight
Strength Lbs/sq. in.
Elongation Percent
Mixture 50 parts of Aroclor 1254
and 50 parts tricresyl phosphate
105,000 70,000
2,987 2,631
290 300
Tricresyl phosphate
50
105,000
2,278
340
70,000
1,779
300
Mixture 50 parts of Aroclor 1254 and 50 parts tricresyl phosphate
Tricresyl phosphate
45
4 5,000 70,000
4 5,000 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
4 5,000 70,000
4 5,000 70,000
3,912 4,057
3.060 3,415
120 180
2)0 230
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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.
>
-.
Specific
Selling Price Per Pound
Material
.
Gravity
In Carload Quantity
Polyvinylchloride ......... 1.35. ........$ .33
Tricresyl phosphate. ....... 1.17..............................
.36
Aroclor 1254 . . ................................... 1.54.............................. ..... . .18
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 Composition
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
$ 1.3 50
1.253 S 0.097 Savings $ 1.355
1.266 $ 0.089 Savings $ 1.360
1.302 $ 0.058 Savings
The results indicate that the Aroclor-tricrcsyl phosphate plasticizer combination offers a saving of 10 cents a running foot when 50 percent plasticization is used. At 4 5 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.
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III. AROCLOR-TRICRESYL PHOSPHATE MIXTURES COMPARED WITH DIBUTYL PHTHALATETRICRESYL PHOSPHATE MIXTURES
Frequently, to accomplish bettej low temperature flexibility and `hand*' dibutyl phthalate or dibutyl sebacate plasticizers are added to tricresyl phosphate.
The data given in Table 111 shows the effectiveness of 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 105,000
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 3.558
Mixture of Aroclor 1254
and TricresylPhosphate
50 parts - 50 parts
Tensile
Elongation
Strength
Percent
Lbs/sq. in.
21i
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 dibutyl phthalate at 35.5 cents a pound in carload quantity was used. The specific gravity value used for this plasticizer was 1.04b.
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 III.
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TABLE IV.
Polyvinylchloride
Molecular Weight
*
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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 dibutyl 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
1.252 $ . 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 dibutyl phthalate-trieresyl 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 50 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
. POLYVINYLCHLORIDE
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 dioctyl phthalate are given. The formulations are typical wire coating compositions. Each contained 100 parts of polyvinylchloride. The amount and type of stabilizer and cJay used in each, form ula was identical.
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TABLE V.
PROPERTIES OF TYPICAL PVC WIRE COATING COMPOSITIONS
Properties
Dioctyl Phthalate
50-50 Aroclor 1262Dioctyl Phthalate
Parts Plasticizer/100 Resin ,
.Plasticizer, Percent Shore A Hardness Tensile Strength, Lbs/sq. 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. 7 Volatile (24 Hr. 105C.)
.
5033.3 82 2710 385 '
1660 -19 .34 .02 75.
5.0 x 1013
4.1
8044.4 79 ' 2475 . 375
1475 -15
0.33 0.05
3` 8.8 x 1013 ' 6.8
The composition containing Aroclor 1262 plasticizer is for 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
Percent Plasticizer
Plastics Costs Per Cubic Foot
Dioctyl Phthalate ......... 33.3
27.04
50-50 Aroclor 1262Dioctyl Phthalate .........
44.4
...........
$
1.70 'Savings
The comparative 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.
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V. CONCLUSIONS
1. It is definitely indicated to utilize Aroclors (chlorinated biphenyls) as plasticizers for polyvinylchloride provided that tricrcsyl 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.
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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 arc
beyond our control. Monsanto Chemical Company disclaims any liability incurred in connec
tion with the use of these data or suggestions.
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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* Char lotte* Cincinnati* Cleveland Philadelphia* Detroit* Los Angeles* San Francisco* Montreal* Tor onto
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