Document 2q4BQ6byg1E7ED96xna4374rp

;1 ; ' . 7 St. Louis Research Report No. 1649 < I $ ' i iNovember 20, 1956, ^ ; Y, -fc. ftt jr-Jt... , si- * Cv'*; -i jS'--3S>'-'Vi5t final report ON APPLICATION WORK ON PRESENT PLASTICIZERS - 1953-54 FLAMMABILITY STUDIES WITH THE SPI TESTER Job No. 2-02-750.01-2616 Part IV Monsanto Chemical Company Organic Chemicals Division St. Louis Research E-'jai Work done by.: -** * Li *: b. 5 by DSW 621005 STLCOPCB4095034 MMI # DISTRIBUTION ,4*- ^ i ' ff * ! File J. R. Darby J. H. Lum - F. B. Zienty - File Duplicate File Circulate: Assoc, and Assist. Res. Directors W. D. Hicks !i. I. Armstrong Plastics Division - H. V/. Mohrma.n Extra Extra Extra This report contains confidential information will oh is the property of the Monsanto Chemical Company end which shall be disclosed only to duly authorised persons. Tr.e recipient is held accountable for the filing and safe custody of tr.e report which must be returned or. 1 ( *f f( ; M | t & DSW 621006 STLCOPCB4095035 rt * ' * * 1 I. INTRODUCTION The problem of accurately determining the flammability of plas tic specimens has been a difficult te3t development program for the plastics industry. Development of the flammability tester by the technical committee under the sponsorship of the Society of the Plastics Industry was a definite 3tep in the proper direction. Because Monsanto had considerable interest in flame retardant plasticizers, such as phosphate esters and Aroclors, it was deemed advisable to organize a complete testing program in order to point up the advantages of these products. It was also desirable to promote trade acceptance of the SPI tester by the industry so that many laboi'atories could better appreciate the value of flame retarded products. An-extensive program of preparation of vinyl films and subse- - quent flammability testing yielded such potentially valuable informa tion for the promotion of our products that a technical paper was delivered at the Third Annual Film and Sheeting Conference in New York. A reprint of this paper constitutes the detailed section of this report. II. SUMMARY Eighty-three plasticized polyvinyl chloride films were calendered at Springfield and extensive flammability tests run on the SPI tester at St. Louis. Overtwo thousand flammability tests were mace. A technical paper was prepared covering these results. III. CONCLUSION'S The SPI tester gave the most defi: lU ve f-vimbilit* results that v;e have beer, able to achiev* 1* promoted for ASTM accc-ptanc< standard tes.. method and a tentative procedure has been developed by this organization. . A truly flame retarded film can be prepared by using as . plasticizers trlcresyl .phosphate, Santlcizersfl40 and 141, 5 and1 other plasticizers `either In combination with the above ones, cr with antlnonv nxide. DSW 621008 STLCOPCB4095037 m 3. Sovaloid C (am aromatic! hydrocarbon) and tri-2-ethylhexyl phosphate gave, f.ame retarded films alone but were rela tively ineffective when1 used in combination with more flammable plasticizers.' 4. Refer to technical paper for other conclusions. IV. REFERENCE TO PREVIOUS WORK Final Report 117-2422, Part II, by P. U. Spink entitled "Sales Service Work on Plasticizers and Resins1' briefly mentions this flammability work. Final Report 117-2414, Part II, by P. W. Spink entitled "Appli cation of Present Plasticizers" (July 30, 1933) also, mentions, but does not detail this flammability program. m Job number 117-2616 succeeded 2414 as the Job number covering "Application Work on Present Plasticizers" and was the Job number to which the cost of the reprints were charged. Parts I, II, and III on 2ol6 were reported previously but did not deal with flamma bility. _ V. DETAILS See reprint at end of report. VI. ACKNOWLEDGMENTS Mi'. G. R. Buchanan suggested this overa'.l program as a means of promoting S-141 sales. Mr. R. R. Lawrence was very cooperative with the calendering program. Mr. E. E. Cowell was co-author on the flammability paper but the print?-? 'r.cd -ei icr-.ly omittec. his name from che reprint. V 7L. APPENDIX Notebook pages SPI tester: concerned t| with - flammability } studies i with the A-27417 to and including A-27A37 t! * \ * ti;rf -= 1 * - <V * 1 ,k m l*3fl If DSW 621009 STLCOPCB4095038 Jrga.Vinnirfc ( A; tel )nstmo It**, ? JI1 i. _r SUMMARY: The SPI tester provides an unexcelled metfiodlfor determining flammability. He retofore unsuspected factors can be meas.ured. The develop S ment of this instrument'i/ilT'vBidoafite'dly'^rove valuable|t6jthe vinyl industry. < ; fit ' f i 7 rI t - Polyvinyl chloride type plastics possess an inherent advantage over many other classes of materials because they can be made flame retardant. Just how great this advantage was could not be accurately assessed until The Society of The Plastics Industry, Inc. through its Group VII Flammability Committee under the Chairmanship of Mr. J.R.Blegen, developed the flammability tester shown in the accompanying photograph. Results of round robin tests made with the first experimental instrument '' ere so encouraging in accuracy and reproducibility that the manufacture oi thus tester was undor'aken by Custom Scientific Instru ments Companv and a flammability specification, based on this instrument, has been written into 'he Proposed Commercis: Standard for General Purpose Vinyl Film by the SPI. Many methods of determining the Flammability characteristics " of plastics had been proposed and evaluated before. However, the SPI Flammabil ity Committee found early that no existing method took into consideration all the significant factors involved in practical application ror foresaw everyday hazards. Results of many of the tests were misleading; invariably they defied reproduction; no single test was accepted as standard. Reported herein are the results obtained on polyvinyl chloride film and sheeting when using an early modefl pCth<| SFjl ter. \^e followed our inter pretation of the general procedures of testing outfineS in tne SPI publication: ' Proposed Commercial Standard - General Purpose Vinyl Film - A Recorded Voluntary Standard of the Trade". i. * lest instrument. A brief review^of the instrument rf11 aidi expla ria.llion of''results to be : give n later. Figure 1 shows a sample holder^and some^of ^he essential feature of th:ee ir.strumenr. The ggaass ssuupppplliieedd IXrr<omfa butane? cvclinder is measured bbyy , means.of the manometer; the^flarnf |^urn| nea^ thjp JaQt of the tester. The the sample holder, f I* V.h * " totde if rac R. Upon arriving a\ the jpoitom end dfithe, track. aesV'itfch. Jctu lector: itfrne j-cflac. :7T le ignition timei i , t itretqhed, acre; IIt& DSW 621010 STLCOPCB4095039 sl&i jl^aXedj ' mea'surec a.ture is registered: d$r? ? ` ?H * -fc ! bcxtipie?jfan t/ *_' / >**A^-* `-|* yfr - J- pyrometer"1 located ?* | - " i"fff i f| * f) ...... The ignition timer registers the time require'd Tor the" flame to travel f |from near the bottom of the specimen holder to the first thread; this reading J Ijthen defines an important flammability parameter, that of ignition time. It is *|pbvious that the burning rate timer measures the time* required for the flame 'to travel six inches, thus providing information on this important factor in flammability studies (burning rate). Temperature developed in the instrument can be taken as a comparative measure of the heat evolved upon burning; this, is a third important flammability factor. Group Classifications: ' One of the complicating features of using the SPI flammability tester is that various procedures of testing must be followed. This complication is well worthwhile because the grouping ol materials into various categories of flame retardance is an important reason for the reliability of the tests. Group 1 was established for materials which vary in burning charac teristics from those which burn readily to those which are slightly flame re tarded. Figure 2 shows additional details of the specimen holder. The test is made with the sample at a 450 angle with a 1/2'' flame emitted from a #22 hypodermic needle burner. The tip of the burner is located 9/16" from the specimen. This group is further subdivided alphabetically from "a" through "d". 5 { !, Group 1-a specifies;the cabinet door be closed. f _ .. - - i 1-b is an open-door test. 1-c required edge ignition with u. or closed. 1 -d is the same as "b" but a measurement of inches burned is called for. iV Groi'o l.I tests<are also made with .r.c -: male at <i30 angle but the needle t i- ^. v - |t $i-.- ^ burner and the'microburrier are both used to edge-ignite the sample while the & cabinet door is closed. Group^II tests are made for materials which will not support .combustion once the^source of heat has been removed. A 2" flame ffrom a microburneij is used'to ignite a 3" x 10" sample supported vertically j^abpve jtlle fiamp -ipigura f|d[deepicts ithe. type ;of holder uded-iTIhese;, tests arc. u|44 IP Klldlf, 11 *t ' f fc'loVed. il -> : '' jt:Pf il !f DSW 621011 L STLCOPCB4095040 *- - y -.v~- ,-- I-<et'-n'dfeS-ec ^clos^ly ^as possiglejo J*"' ~ 5 AFryv*.c,5y less. |asesl noted j ` f PI i i ' m - *WWV!-# W- -fc * 5 1 Film samples wereftut tb 3" x 9' sta HW&- ' - [ FS iiditi oned 3 hrsilir'anpS e-S: . >. > } - ^ - -j- ;*?<-*! *.S fair circulation oven at 50C., then cooled'lnTa'5r Seator before testing^ For Group 3 tests the sample length was increased Effect of Plasticizers: $ *4. . & A series of 10 different plasticizers at 50. PHR concentration was test ed for flammability in every classification. At least five samples were tested on each formulation in each classification, and whenever results varied by over 50% from the mean, additional tests were 'made until agreement within a series was obtained. Table I contains the average results for each formulation. Dioctyl sebacate imparted the fastest burning rate and burned by every test. Dioctyl adipate and dioctyl phthalate were possibly the next most flam mable Santicizer 160 (butyl benzyl phthalate) was slightly less flammable than the aforementioned plasticizers. Paraplex G-50, which exhibited a slow burning rate, was completely consumed whenever ignited and developed ex cessively high temperatures. This was the only plasticizer which gave an afterflame in test V3, which means that the film continued to burn after re moval of the ignition flame. (The other flammable plasticizers had been burned out during the 10 seconds flaming time.) "t-i r Tricresyl phosphate, Santicizer 140 (cresyl diphenyl phosphate) and Santicizer 141 (alkyl diaryl phosphate) were quite flame retardant. Sovaloid C, | a petroleum hydrocarbon cut, showed surprising;,f|ame retardance. Trioctyl- ~ phosphate was the least flame resistant of those compositions which did not burn completely. It is interesting to note that ignition time in seconds given under j-r^u-s i-a, b and d, and c was not significant in ir.d: ating w' .'-'r the compos'tior would burn completely. Thus, Santicizer 141 ^.cve^iu ignition time of.?. ,1^, J seconds but was se lf-extingui shing. whereas,flJOf^gave an ignition time of v ?.3 and burned all the way. The times denoted injthe table under seconds - ?- * $ < f a * ' .. burning have a different significance when "boxedj|n"l All Jthese compositions were self-extinguishing and the figures cited ^re.flhe seconds burning before F^gt|s^^ent2As|pi^iou^ic^>lain?d. au,|f a^thi ^mi i | required: foor the|flarne t^|rav'el 6 '. In co|um|iu'ig"r|groi|ps b and*ri, the- | j inches ^burned are ;ecorded|as well as the . 4fH uiredito' burn this distance, tss DSW 621012 STLCOPCB4095041 i: i ' f>'I Effect" (cent ration: Tat of. increasing the concentration ot 4 plasticizers from.40 to 70 PHR by increments of 10 PHR. We*were unable to find significant:differences in the DOP compositions. It was thought that the burning ratelwould become faster with increasing concentrations.of plas ticizer, but this^relatibnship was not detected. The most noticeable'trend developed was the elevation in temperature with an increasing concentration of DOP. It was surprising that the 40 PHR dioctyl phtl.alate film burned at the comparative fast rate of 4.6 seconds. This series of samples were re tested later. Increasing the concentration of Santicizers 140 and 141 had very little effect on any test. Trioctyl phosphate became measurably more flammable with increasing concentrations until all the specimens were consumed at 60 and 70 PHR concentration in the Group II test. It is noteworthy here that in Group II tests a temperature increase of 40F. developed from the ignition flame alone. Effect of Plasticizer Mixtures: It is when testing a mixture of plasticizers that we bring out the prac tical flame-retarding efficiency of plasticizers. By holding constant the con centration of plasticizer at 50 PHR, using DOP as the building plasticizer, and then adding flame retarding plasticizers, we can assess this factor. Table III shows that 10 PHR of tricresyl phosphate or cresyl diphenyl phosphate (S-140) produces a self-extinguishing film.,A proportion of 15 parts of, Santicizer 141 with 35 parts DOP is self-extinguishing. As much as 20 parts of trioctyl phosphate failed to effect seli-exting :i shincni. Neither chlorinated paraffin (Chlorafin 42-S) nor Sovaloid C, at 15 parts, Drevented the film from burning. Effect of Film Thickness: ~ $*>> ~ j '" ; ' ' When a 50, PHR DOP plasticized composition was increased in thick ness from *4 mil^through^, 12 and 20 mils, definite trends were established. Both the time reqjiired for ignition and the time measured for burning 6 inches, thi.cjci|e.s^| mcr^ased.|T,he temperatur^ ^egi in ` the . c.*-a*binI e*t generl ` . became higher as more fue1 was charged ij .. of thicker Compositions.! I the forni DSW 621013 STLCOPCB4095042 , ___JStpmpSB^M|tnc reaSingTdimcenti . _ pNhsii further enrauvlhg ?lame relardance. ^2 oxide flam^tarded all type"s^and mfx^lr^lfoT^l&ItiCi the' opacifying, and pigment covering prope^e|||^irntirnon5 tolerated, such as in white opaque film and 'sheeting, flamdlrtet antimony oxide is another way of achieving'this desirable pro s * * * -v amm %i M.9rf0 Table V supplies the detailed data on these tests. Itti. Vinyls. Effect of Fillers: ' j - __ ^ m' Table VI contains information of the flammability effects pfj.calcium carbonate and titanium dioxide when added as fillers. Increasinglythe concen tration of Atomite (calcium carbonate) filler accelerated the btirning rate and diminished the ignition time when DOP was used as the pli^icizer. With a 35 PHR DOP-15 PHR Santicizer 141 formulation, a similar increase in Atomite content had no definite effect and all stocks were self-extinguishing. The flammability effect of 5 PHR of Atomite or titanium dioxide was min imal with all plasticizers tested. It would be interesting to investigate the f'effect of carbon black on flammability. . ? Miscellaneous Factors: The change of stabilizers from the lead type to the epoxy^ilus barium- cadmium type had very little effect except for prolonging the burning rate of the dioctyl adipate film. , ;; . Vinylite VYNW (95% PVC / 5% PVAC) appeared toW^^pfery5slightly more flammable than straight polyvinyi culcri^e. Shortir lilffiiiu^ rates were observed for tests 1-b, c and d, and also for Group II w|^E!using DOP as the plasticizer. DOP in this resin could be readily flarne'retarded with phosphate plasticizers and with antimony oxide 5t After having run about 2500 tests, (luring the coursej ; everal parts of the tester were repaired or replaced, ths.fii ine with various concentrations of DOP was retestedrin CRisj j. .. . j{ ' ,,: W j. show somfewhat longer burning times than determined prert.o{ rHHiR d__b__m__l _itton wa,s, howev.cr .isti 11 ithelmoste rapid (burr t * WW ~ Jt * ? * - I * - I Ml- (r f t.-S nnot de terrtiijied|whether4an aging; effect on;thefiim can. be the, condit; is of the tester have changec ' yjLi ms lit iiiil ' I ~\les deal- [Results- " I* " (have i Ik W&? It | rted ill DSW 621014 STLCOPCB4095043 tma >rdei spring fstoi $e|he vari able.humldi t y factor oifith^burmnS'pi :asionS ^-/-h--e---n--?3<ScS'JPal rs ant* S"ght changes ln^the instru- y >n 9^gnificant thanges in the burning rate or ignition time of l^standard" specimen. ' I: i 1-. ?; ' i -f. y 4^ .. . . r -y ; ;i- ... . .% - i >'4 -8 One.measurementwhich almost invariably proved reliable was that of determining if the composition was self-extinguishing. By using as a criterion the amount burned, rather than the rate of burning, ve-y clear-cut and defin ite results were obtained. These results are illustrated in the photographs of the plastics, specimens after burning. Although variations could be detected between the burning rates of several "flammable" compositions, the profound difference between films was simply whether they continued to burn or not. Samples of commercial film from six different manufacturers were evaluated with the tester. Two were found to be effectively flame retarded, three had burning characteristics resembling those imparted with phthalate plasticizers, and one was almost completely consumed, thus suggesting the presence of a proportion of a polymeric plasticizer. It so happened that the most flammable film was described by accompanying literature as having some outstanding property other than flame resistance. All commercial films passed the flammability specification of a 5-second minimum burning rate as proposed by the SPI. All formulations in this ex perimental series which registered a burning rate of less than 5 seconds were reviewed. Upon re-examination after aging, no film burned in less than 5 seconds. ft i ; * * s. * > " * *' 4 It therefore appears that the proposed SP' specification can be met by almost any vinyl formulation. ii tf Future of the SPI Tester: ^I v `. .. ^ ^ . ' \ i r-* ' The SPI tester provides an unexcelled method for determining flam - rnabiiity. It will undoubtedlyjprove valuable to the trade. Probably, specifications foE flame retardant films by legislation in the future will increasingly call -'4 3 *$.- v .- *ii. A > 4. > - OJ : uporfc tjiis tester.; The ASTM ha started machinery in motion to de-I * ` - ?i- w ' f * .. p- i'- " sWtjmfeth1o1d*f1or; tfhflsldfilsfi 1 i MMf M f- 4` *1 . v rW - - / t * *>4 4 ft another advantage liktdy to acc /ief development of this DSW 621015 STLCOPCB4095044 'j?' -rf :. 4., . S' . # -'4 - % - ?, t 4#? 4V The materials indicated in this paper by trademarks are supplied by the following companies: Vinylite Atomite Paraplex Sovaloid C Clorafin 42-S Plumb-O-Sil Ma r k( stabi lize r s) Opalon 300 Santici ze r Bakelite Corp. (Unit of Union Carbide & Carbon Corp.) Thompson-Weinman and Co. . > . Rohm It Haas Co. Socony-Vacuum Oil Co. ). ' Hercules Powder Co. National Lead Co. Argus Chemical Lab. Monsanto Chemical Co. " Monsanto Chemical Co. fe* - - ^ iI i`4 tipilefU| 1*14? I i: | |f i Hi 11h|14? 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