Document 9JzeRQ1Y9M61oQLro1nymr04R

St. Louis Research Report No. 1280 June 50, 1955 < SPECIAL APPLICATION REPORT ON PLASTICIZER SALES DEVELOPMENT RESEARCH - 1955 PART I: THE MONTARS Job No. 2-02-750.01-2892-1 Monsanto Chemical Company ^ Organic Chemicals Division. St. Louis Research Department STLCOPCB4094855 DISTRIBUTION geof report no. 1280 1. File 2 J. R. Darby - 3* H. K. Nason ^ Duplicate File 5* Circulate: Assist. & Assoc. Re3. Directors - Safe Deposit^--' 6. 0. R. Buchanan - 7. H. I. Armstrong 3. Dayton - eventually ' 9- Extra 10. Extra 11. Extra i T..ls report contains conrr.fider.tlal information which Is the property of the Monsanto Chemical fCompany and which shall -be-dlsclosM only .o duly authorized personflns. The recipient is held accountable for the filing and safe custrccody of the report, which must h returned onjidemfianidIv ,t i i. .t . ,` " I' STLCOPCB4094856 STLCOPCB4094857 K'tx ! Ft f. f INTRODUCTION 'f In the production of the Aroclors and Santowax R, residues from the distillation phase have been collected and then discarded. These residues, named Montars, have been assumed numbers (1 through 10) more or less corresponding to their parent compounds. Table I. Chemically, the Montars are polychlorinated polyphenyls. Their chlorine content varies from 28 to 57# and their calcium oxide con tent from 0.8# to In 1953 the average monthly production of Montars was 182,000 pounds with Nos. 1, 3, 4, and 5 accounting fur 60$6 of that amount. At the present time the Anniston plant pumps the residues to a dump while che WQK plant must drum and haul them to a dump. The cost of these methods of disposal is estimated at 0.25 to 1.2 cents per pound. Mention should be made then of the dollar advantage to Monsanto of selling these compounds, in preference to the present cost of disposal. SUMMARY The Montars were tested as replacements and extenders for asphalt in adhesives and other asphalt applications; as fire retar dant additives to asphalt formulations, to polyesters and to poly vinyl chloride formulations. Laboratory test results indicate that the Montars have applica tion possibilities in each of the above categories. Because Montar No. 9, a residue from Santowax R, does not con tain chlorine, it was not Included in the tests. CONCLUSIONS Laboratory test data indicate that: 1. The Montars, if sold at about $0.05 per pound, are'the most inexpensive source of organic-combined chlorine presently available. Table III. Other organic-combined chlorine compounds sell in the 16-18^/lb. range. 2. The Montars are soluble in most aromatic solvent and are especially soluble in the kerosene-type solvents/ Table IV. 3*. The Montars are compatible with asphalt ^up to two parts .ofj Montari ta^ or\e|part o^ .ajjphalt. t i s " 1 `* v t 3 . lilWJ hi1 :coi DSW 620830 mm STLCOPCB4094858 _ . \ $- - -T ' t~ `'*' ' * V: . -` 6. They are compatible in polyester formulations and impart some flame retardancy to those formulations. RECOMMENDATIONS ' Montars should be stressed as inexpensive sources of organiccombined chlorine, as extenders and replacements fOr asphalt and as flame retardant additives to asphalt, polyvinyl chloride and polyester formulations. This information could well be Incorporated into a technical bulletin on the Montars and their application. PATENT STATUS Items of a patentable nature have been precluded by early patents covering the application of chlorine-containing organic compounds. EXPERIMENTAL Production of the Montars, being geared to that of the Aroclors and Santowax R, will vary from month to month, and as a result, no specific amount is produced each month. The figures In Table I, though for the year 1955, held true for 1954 with the exception of a decrease in No. 4 and a like increase in No. 1. TABLE I ` AVERAGE MONTHLY PRODUCTION OF MONTARS Montar Parent Compound IN 1955 Percent Residue Pounds Produced ! i I % t aoi Aroclor 1242 Aroclor- 1248 Aroclor 1254 Aroclor 1260 Aroclor;S460 Aroclor ^465 Santowax R My ie of* fi 15 2S 60C 4,000 20,000 28,000 45.000 320 60.000 f DSW 620831 w' r -W STLCOPCB4094859 Montar brown solid brown solid brown solid 120-170C 298C None at 4 brown solid 14o-200C 343C. 5 black solid 180-250oC. 6 black solid 150-210C 9 black mass 130-160 C 2c'7C 304C. 10 black solid 140C. Data obtained from Montar Data Sheet The salient feature of the data in Table III below is the quantity of organic chlorine to be found in most of the Montars. To the best of this writer's knowledge, they are the least expen sive source of organic-combined chlorine available. TABLE III TYPICAL CHEMICAL ANALYSIS 1 Montar Chemical Name Chlorine Calcium Oxide % Iron polychlorinated polyphenyl 40.5 2 polychlorinated polyphenyl 46.2 polychlorinated polyphenyl 51.6 polychlorinated polyphenyl 55-4 polychlorinated polyphenyl 57-59 polychlorinated polyphenyl 58.6 polyphenyl 0 mixed Jo| 5sard No. 9 28 . 0.12 1.8 3-5 6-9 4.5 2.0 0.8 2.5 i 0.07 , t * 0131 * * 0.12 i 0.13 I \ 0157I Solution data on the Montars show them to be very soluble|if solvents and soluble in kerosene ".type solvents " th iMohtat si STLCOPCB4094860 *.$ * % i I# SOLUTION bATA Montar unatic* Kerosene Type Methanol Acetone VS VS VS VS 5 VS 6 VS 9 VS 10 VS S SS VSS S SS VSS S SS VSS S SS VSS VS SS SS vs SS SS SS I SS SS I SS Such as benzene or toluene. KEY I Insoluble VSS Very Slightly Soluble SS Slightly Soluble S Soluble ' VS Very Soluble EXPERIMENTAL - Potential Application A. In Adhesives A 50$6 solution of Montars 2, 5 and 4 in Velslcol 50 mixed 1:1 with a 60$-solids, rubber emulsion provided good tack when tested as a paper adhesive. The tack appeared to be as good as that obtained when using a 50^ solution of asphalt in kerosene. Other Montars, tested in similar fashion, gave comparable results. To 25 g. of the above Velsicol solution, 1.25 g> and 2.5 g- of an emulsifier was added. These mixtures were then diluted with water. The Bample containing 5% emulsifier remained in an emulsi fied state until it was diluted 160% with water. The one contain ing IO56 emulsifier did not break until diluted 30^ with water. 4i ` " These test results tend to show that the Montars could re place or extend.asphalt in the adhesive field at a saving to the formulator, because they provide equivalent tack, are equally solu ble arid emulsify*Well. * tB.| Alf|ek'a<FMlamIeI- Retardant IfH Additive - f 3^ of Montari i&iaj&i W fff* m DSW 620833 nI STLCOPCB4094861 | f*- ft SMi r-?f Using the stir-in technique, varying amounts "of crushed Montar 4 were added to molten asphalt, and the mixture was heated to 190C. to effect solution of the Montar. A portion of the mixture was transferred to a crucible and the mixture was heated until the fumes would ignite (approximately 200C.). The time required for the flames to self-extinguish was then measured. The results follow: TABLE V FLAME RETARDANCY OF THE MONTARS Composition Flame-Out Time Asphalt, per se 10% Montar added 20% Montar added 30% Montar added 50% Montar added 67% Montar added 210 seconds 90 seconds 10-20 seconds Instantaneous Instantaneous Instantaneous The flame-retardant action of the Montar was caused by the ~ formation of an lntumescent layer on the surface of the mixture, snuffing out the flame- This action could be utilized In the production of film and sheeting, such as floor tile, where the limitations of the Montars due to color are not serious. C- As An Extender for Asphalt The compatibility of Montars in asphalt was determined by nixing and heating the mixtures to effect solution. Montars are readily compatible at least up to the ratio of 2 parts Montar to one part asphalt. It was noted that as the concentration of Montars increased the softening point and the brittleness of the mixture also in creased. ' f . D. As A Flame-Retardant Additive to Polyesters l i Montars 2, 4, and 6 were added to a series of polyester formulations with the Montar concentration being 1%. , These .forrau- Unch squaresi whl( isus ted 1vis dalill Rate DSW 620834 STLCOPCB4094862 m ? i'i ? 4* * Since the color of Montar* 1* dark brown to black, their use in vinyls, in adhesives and in polyesters is limited to those applications where the color of the Montars is of little Importance. However, with an estimated selling price of 5^ per pound, the Montars should certainly be attractive as an inexpensive source of chlorine, as an extender or replacement for asphalt and as a flameretardant additive. ACKNOWLEDGMENT The writer is Indebted to Dr. A. Martin Ellenburg for produc tion and physical and chemical analysis data and to Mr. C. F. Bourbeau for tests run on Montars in polyesters. APPENDIX ' "" ' - Laboratory notebook pages 50451 and 59452 In Book No. A-1170 issued in 1954 to R. M. Parks. ' R M. Parks J. R. Darby * l ?-j'* I * i > t f t k t r f s. DSW 620835 STLCOPCB4094863