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f St. Louis Research Report No. l?8l May 16, 1955 i -; * is mi FINAL REPORT ON SCREENING TESTS ON MONSANTO AND COMPETITIVE PLASTICIZERS - 1954 PART I: THE INTENSIVE EVALUATION OF SECONDARY PLASTICIZERS INCLUDING THE AROCLORS Job No- 2-02-750.01-2821-1 *t i Monsanto Chemical Company Organic Chemicals Division St. Louis Research Department Pa 'ks ! i: I DSW 620811 I* STLCOPCB4094839 m i m mi IIP Ml DISTRIBUTION OF REPORT NO. 128l File J. R. Darby H. K. Nason - File Duplicate File Circulate: Assist. & Assoc. Res. Directors - Safe Deposit G. R. Buchanan H. I. Armstrong Dayton - eventually ' Springfield - H. W. Mohrman T. M. Patrick Extra Extra This report contains confidential Information which is the property of the Monsanto Chemical Company and which shall be disclosed only to duly authorized persons.. The recipient Is held accountable for the filing and safe cu3todyfoff the report, which must be returned on demand. ; I U> DSW 620812 II11 l f 1 STLCOPCB4094840 STLCOPCB4094841 pl INTRODUCTION r$ Stf lUfl A project of evaluating secondary or extender plasticizers has ; been undertaken with a two-fold purpose. The first is to learn the " good points and the limitations of secondaries currently offered to the trade. The second purpose is to study the properties of Monsanto Aroclors (chlorinated biphenyls) and in turn attempt to find a place for them in the secondary market. There are currently two main classes of secondaries: the chlor inated paraffins and the aromatic hydrocarbons, products of oil fractionation. Both classes of compounds offer advantages in price when compared to the primary plasticizers, but they also have serious limitations of use in vinyl formulatioT.3. This report, then, is a study of those advantages and disadvantages, and includes a study of the Aroclors. SUMMARY So far nineteen secondaries, including the A"oclors, have been evaluated in relation to their performance and permanence as the __ _ sole plasticizer and in combination with a primary plasticizer. Preliminary evaluations were made on the secondaries at 67 and 50 PHR and at 1:1 DOP and 1:2 OOP. In addition, heat and light stability, flammabllity, soapy water extraction and electrical tests were made on the secondaries at the compatibility-limit point. CONCLUSIONS The Conclusions section is divided into two parts. Part I com pares the chlorinated paraffins to the Aroclors and HB-20, since they are competitive in performance and price, selling at 15 to 22 cents per pound. Part II is a report on the other secondaries studied to date, those which sell from 5 cents per gallon to 15 cents per pound. Part Test results indicate that: 1. The Aroclors and HB-20 are more compatible and are faster fusing than the chlorinated paraffins. The limits of compati-. bility with DOP for*the Aroclors andiHB^O is 1 part secondary to 3ft parts DOP. For the chlorinated paraffins the limit is 1 part chlor inated paraffin to 6 parts DOP. Table I, Part I. STLCOPCB4094842 ' ,- , # * ; 4ST* i*.W U ' Hy' . - ' '' ? 4. The chlorinated paraffins are superior to the Aroclors and HB-20 in these respects: they are much less volatile, are less extractable by soapy water, fume less while milling and produce compositions with less odor in kind and degree. Table I and II. 5- The vapors given off while roll-milling a composition containing a liquid Aroclor are pungent and toxic. The products, therefore, should not be used in a room that is not well ventilated or evacuated. 6. Both HB-20 and the liquid Aroclors seem to have a bene ficial effect on viscosity-stability in plastisols by slowing down . viscosity buildup. Table III. Part II The chief attribute of the aromatic hydrocarbons, when used in vinyls, is a low price. Except for Cabol 100 (G. L. Cabot Co.), they will not form a sheet on the roll mill and have very limited compatibility when mixed v/ith DOP -1:6. Generally, they are very dark in color and fume heavily while being roll-muled. The fumes given off are extremely pungent. Since they are dark-colored, their heat and light stability are poor and they are limited in use to compositions of dark brown or black color. Table I, Part II. RECOMMENDATIONS The program of evaluating secondaries should be continued be cause more compounds in that category are appearing on the market and because Monsanto, with its Aroclors, HB-20 and HB-4o, has a stake in the secondary market. PATENT STATUS Nothing of a patentable nature has been discovered as a result of this project.i , * i t , s i* ' PM * 5 M . , * j - * f I t ' EXPERIMENTAL WORK 1 t relimlr llries ;yaj ila|tion$ ,ol l the! Yt i; DSW 620815 STLCOPCB4094843 fei i- 1 r i . ^That hB-ho? Hff-20 and the Aroclora are much more eompati (via the Loop Test) than the chlorinated paraffins. HB-4Q is eoa- patible at 1:1 DOF and HB-20 and the Arodora are compatible at 1:3 DOP, whereas the chlorinated paraffins are compatible at only 1:6 DOP. . 2. That the Aroclors and HB-4o alone, or when mixed with DOP, are faster fusing than HB-20 and the chlorinated paraffins. 3- That the Aroclors are less extractable by kerosene than HB-20, HB-40 and the chlorinated paraffins. 4. That the Aroclors and HB-20 v'hen incorporated In plastisols do an adequate job of slowing down the buildup of viscosity. This element of low viscosity buildup should be of importance to the user of plastisols for glove dipping and some cloth coating. 5- That all of those compounds listed in Part I are essentially equivalent in flexibility and water sensitivity. 6. That the chlorinated paraffins are less volatile and they fume less upon milling than the Aroclors, HB-20 and HB-40. The fuming and high degree of volatility are the major drawbacks to the use of the Aroclors and HB-20. ' __ T. That the chlorinated paraffins produce compositions with less odor than those of the Aroclors and HB-20. HB-40 is nearly median in that Instance. Test results in Table II Indicate that: 1. The Aroclors-are slightly more flame retardant than the chlorinated paraffins and much more than HB-20 and HB-40. 2. The Aroclors and HB-40 are more heat stable than the chlor inated paraffins and HB-20. 3- They are generally equivalent in light stability; however, HB-20 is very poor in this respect. They are also roughly equiva lent in electrical properties. 4. The chlorinated paraffins are much less extractable by soapy water than are the Aroclors.* * Preliminary data !in Table I, Part II indicate'that the' aromatic hydrocarbons suffer from: Poor initial fcolcr .and odor "i............................ II i- i 4? its ,af! ems if DSW 620816 STLCOPCB4094844 lift ''V* V 5 * V1 l >' I: =? 1 . -A 4. A high degree of fuming while milling and the fumes given off are rather noxious. However, they are inexpensive and probably do find use in low- grade, black formulations where their deficiencies are less noticeable. In summation then, the Aroclors, HB-20 and HB-40 do show several distinct advantages over the chlorinated paraffins and the aromatic hydrocarbons which should recommend them to users of secondary or extender plasticizers. However, the incorporation of the Aroclors and HB-20 in vinyls must be limited by their fuming, their volatility, and the toxicity of the Aroclor fumes. DISCUSSION To give the reader an idea of the wide range of selling prices the following is quoted from the price lists of the companies con cerned : HB-4C Aroclors . Chlorinated Paraffins HB-20 Aromatic Hydrocarbon Aromatic Hydrocarbon 22(^/lb. l8^/lb. 16-17.5s^/lb. 15^/lb. O.05J/IX). 0.05^/gal. The range of prices shown above and the evaluation data found in this report gives the potential formulator an extremely wide choice of extenders for his particular use. It becomes necessary then for the buyer/user to select a secondary carefully and for the seller to approach the buyer equipped with all data showing the abilities of the secondary with sufficient warning about its defi ciencies. A user could easily get into difficulties of major severity If he employed some of these secondaries indiscriminately. ANALYTICAL PROCEDURES All testing in thl3 report was done according to the "Standard Test Methods of the Plasticizer Application Laboratory." i* f | u DSW 620817 STLCOPCB4094845 STLCOPCB4094846 STLCOPCB4094850 STLCOPCB4094851 STLCOPCB4094852 TABLE III mv HEAT AND LIGHT STABILITY Qeneral Formulation Opalon 300 100 Plasticizer 66 (1 pt. secondary to 5 pts. DOP) * DS-207 0.75 f1 -------------------------Aroclor 1232 12^2 1248 1251* llorafin 4o 4o\r 42 42S Ihlorowax 4o 70 lalowax 4oo4 Panaflex BH-1 Minutes to Degradation* 60 60 60 60 40 40 40 40 40 40 40 20 Hours to Degradation** 300 300 400 200 200 200 300 200 300 300 50 50 *At 170C., normal heat stability test. **In the Weatherometer. ' * -1 fit ^ Parks - - '\ yj------ ' ' DSW 620825 STLCOPCB4094853 i appendix^ lV Aroclor - Chlorinated biphenyl, Monsanto 1232 - 32j6 chlorinated 1242 - 4256 chlorinated 1248 - 48# chlorinated 1254 - 54# chlorinated 2.' HB-20 - Partially hydrogenated polyethylbenzene from Texas City still drainings. 3- HB-40 - Partially hydrogenated terphenyls, Monsanto. 4. Clorafin - Chlorinated paraffins, Hercules Powder Co. 40 - 4o# chlorinated 40V - 4o# chlorinated 42 - 42# chlorinated 42S - 42# chlorinated, stabilized 5. Chlorowax - Chlorinated paraffins, Diamond Alkali Co. 4o - 4o# chlorinated 70 - 70# chlorinated, a solid 6. Halowax 4004 - 4o# chlorinated paraffin, Carbide & Carbon. 7. Dutrex - Aromatic hydrocarbons. Shell Chemical Co. 8. Cabol 100 - Aromatic hydrocarbon, Godfrey L. Cabot, Inc. 9. Solvalold C & K - Aromatic hydrocarbons, Socony-Vacuum Oil Co. 10. Panaflex BN-1 - Aromatic hydrocarbon, Pan American Oil Refining Co. Laboratory Notebooks Pages A-96817-8 A-46842 A-46823 A-53454 A-46827 A-58455 A-46837 A-58458 issued to R. M. Parks in 1951* in laboratory notebooks i( t r SB. > \ I* k \ || m F if Is\ n \ 'W- 1 IIfIIIIt[i|4|[ it f plMlijf j A; 1 >jf I; jIL1.1M Ii f;l||m r , i. > f f ^ I ;* tFrfcsfl f.i if [ tI ' >\ 1i iF [If - ' >i r , 1] m. Ww m Ii|I : It i^ v1ft ;;;: ? "f- 1 jl [ p;: 1 - if ? 1f ^* L f ILft.ia i L S . 4- DSW 620826 , ,; i1 If i 1m j. mi- > i; 1 * # ' ! f1 * i STLCOPCB4094854