Document RJMv4LM3DDxXDevJBYbbe47aa

?Y >; .j *: f5 V' f*f & 1 A ' vi*#. v t ;-v*a 1 S-i fcr'-S V ? # FINAL REPORT 4 ON V APPLICATION WORK ON PRESENT PLASTICIZERS, 1955 PART II Job No. 2-02-750.OI-2S96-II 4 rf i h Monsanto Chemical iC^mpany Organic Chemicals Division St. Louis Research!Department Work^&one by: s-f s I ?i J. R. Darby W. G. Allen J. A. Cannon A. Yy. CCoorarann ,, $ il ; P. R.! Grfeham? f fmt 4 * I L. R. Wangler < ? l 1 L , . ?1 l1 s ' f HjffI |ifft If ; Wrltten|by: P. R. Graham . r! ' %i M Pf ILtI 1ii 1ii*" I f 5- * * t H ! f ' Sf | ? 4 i i DSW 620973 STLCOPCB4095001 This report contains confidential information which is the property of the Monsanto Chemical Company and which vha*.3. ' e disclosed only to duly authorised persons. The rc y i; en-: . j ..CiU acceptable for filing and safe custody of the report which must be returned j'~ demand. i* s s lM , > f STLCOPCB4095002 I. INTRODUCTION 4 PageINo. A II. SUMMARY . . . III. CONCLUSIONS . rv. FUTURE WORK . V. PATENT STATUS VI. REFERENCES . VII. TEST METHODS VIII. DETAILS . . . A. Application of Primary Plasticizers ............................. 1. Preliminary Evaluation of the Santlclzer " oOO Series..............................................................................5,6 2. Comparison of Santicizer 605 to Flexol426 . S 5. Comparative Evaluation of Santicizer 615 and DfJODP............................. 6,7,8 4. Replacement of S-oCl with a DIDP/DIDA/DIOP Mixture....................................................................................... 3,9 5- Volatility of Butyl Decyl Phthalate vs. Competitive Products ..................................................... S 6. Comparison of Santicizer l'il to Ohio-Apex RS-1313 ....................................... .......... 10 7. Comparison of DIDA to Morton Withers' Morflex P-20.........................................................................1C 3. Intensive Evaluation ~ ' ??* TT-'J......................... 10,11 $. A Study of Kerosene Extraction of DOP and DIDP Formulations...............................................................11 10. Extended Volatility Tests for,Both Monomeric j. ,, and Polymeric Plasticizers . . \ l................... 11 11. Low Temperature Properties of Plasticizers . 12 B. Application of Secondary Plasticizers|. . ,. ; ; " ? ?1. ' Intensive ^Comparison _! f^^cl&xls'lo' ^cfeipiti| | f * tlve Chlorinated Paraffins . . . f ... . . 12,13 2.( Light.Stability of HB-2q 4., ; i.; I :.|4 .f., i , l 3.| ^yalultipii. of ^adtliUzj 1 * DSW 620975 4 STLCOPCB4095003 an* w :$ ' M 11 Evaluation of New Process Plasticizers I 4* _ - 1. New-Process DOP from Everett Plant....................15 2. New-Process Santicizer 160....................................... 15 D. Intensive Evaluation of Santicizer 213 ..... 15,16,17 APPENDIX - I .... .................................................................................... Notebook Pages ....................................................................................... 17 APPENDIX - II.................................................................................. .... Curves and Charts (See end of report) .................................. Chart No. I II III IV V VI VII i -j VIII IX X Properties of Plasticized Opalon 300 Containing the Santlciter 600 Series Properties of Plasticizers Volatility Per 3e:S-laO (lopped) vs. 3-160 (Standard) Kerosene ExtractXon:DOP vs. DIDP Properties of Plasticized Opalon 300 Evaluation of Santicizer 601 Evaluation of Santicizer 601 Light Stability of HB-20 \ t *> Comparison of the Properties of Standard Santicizer 160 and Distilled S-160 Properties of Plasticized aud Containing Santicizer 213 i I* M* H H-MM- ' 1 * tMi ;- ' ` 1 ?. f *' I * M {' DSW 620976 STLCOPCB4095004 *4 ;* 3IXJCT] Wherl responsible f6r"Jfoe*company-wide testing of exploratory andlccmmercial organic congpu^ds as potential plasticizers, a well defined screening syscem oust be employed. The first phase of thisfoperation i3 the preliminary evaluation, to which every compound!is initially subjected. Upon occasion, promising compounds emerge from this preliminary screening and are then submitted to the second phase known as the intensive evaluation. In the intensive evaluation stage these compounds are given a more thorough examina tion for properties required in specific applications such as plastlsols, vinyl foam, electricals, etc. Generally when the applications are large ones the work Is separated into specific classifications with individual Job numbers and appropriations. However, a large amount of the Intensive evaluation is of a general nature and does not fit well into any of the specific application categories. This report comprises a compilation of the general application work completed during 1953 and is Included as Part II on Final Report No. 1J11 under Job No. 2-02-750.01-2896-1. (Ref. No. 1) From time to time, the Sales Department has been given this application data to furnish them with valuable technical lnformation in their customer contacts. ` II. SUMMARY Because of the diversified nature of the contents of this report, it is divided conveniently into four main classifications: 1. Application Work on Primary Plasticizers 2. Application Work on Secondary Plasticizers 3. Evaluation of New Process Plasticizers 4. Intensive Evaluation of Santicizer 2.33 The work on primary plasticizers Ir.j lades an evaluation cf the physical properties of a large number i th. ';^ plasticizers comprising one Santicizer oOO series. _n some cases, a specific member of this series is compared directly to its closest competi tor iii the trade. Also Included in this category is the work } involved in finding a replacement for DNODP ^di(n-octyl, n-decyl) pnthalate7 which became scarce due to a restricted alcohol supply. Other studies on primary plasticizers reported herein are: the, comparison of DIDA to Its competitor Mcrflex P-20; an Intensive evaluation of. Flexol|,77G (dlpropyiene glycol .dibenzoate). - ^cbrnneti- tor> for Santlblzb#-loO:* permanence put-parties of-a number off pXas- " ticlzers; and a fundamental study of tne low temperature characteris tics of plasticizers^ hi DSW 620977 STLCOPCB4095005 I.] reported in* fm_,.. 4 . _ piastfcleers^was arlfer*report (Refv1l),' additional information was: obtained in|1955 >This includes ;a conqcarison of the Aroclors to competiti e Chlorinated paraffins,% light stability work on HB-20> ^and * evaluation of Santicizer 212. * f#i Application information pertinent to our plant processes are also included for the charcoal treatment of DOP at Everett ar.d the laboratory distillation and topping of Santicizer l6o. Additional application information on Santicizer 213 and summary of its properties complete the final section of this report. The original work on floor tile evaluation was Included under this Job number, however, the importance of the work warranted its separation under a separate Job number (Ref. 10). III. CONCLUSIONS ( 1. Santicizer 603 (DIDP/DBP S0:20) Is equivalent to Flexol 426 (Carbide's butyl octyl phthalate) In all properties except light stability where Flexol 426 is superior. These two products are direct competitors in the trade. _ 2. Santicizer 615 (DIDP/DIDA 3:1) Is the only mixed plasticizer found which compares in plasticization properties to DNODP. However, this mixture and all DIDP-DIDA combinations have lower compatibility limits than DNODP. This relative incompatibility poses a problem in its usage and Indicates that caution must be used during formulation. 1 ' $ | *f 3. A mixture comprising 37.5# DID?, 12.5# DIOP, 50$ DIDA may be used as a replacement for Santicizer 601 (DN0DP/DI0P 1:1) in applications where S-601 was recommences. When .'clr'g this mixture most properties are equivalent, however z ~< "-orifice in lc temperature flexibility, water resistance and neat stability must be expected. > , 5. .1 \ k r4 ' 1 i ;| 4. Ohio-Apex plasticizer RS-1313 (probably a mixture of tri- cresyl phosphatefvrith a fatty acid ester like butyl oleate) Is definitely-, less Compatible than Santicizer 141. Moreover, the competitive ^mixture is decidedly less light stable than S-141. This dlsqpvery,chis definitely stopped jtha early competition er.- 5 counteS^e(||?rttppB4l9^5 in flame rd3lstLx.nr formulations.1 * i. *! DSW 620978 ?* * ! STLCOPCB4095006 '-o .. . . Tedl^eilQl^rerv^lR^repei , In fact/ slightly superior in low temperature flexibility.I f 6. Flexol 77-G fuses readily, its rate of fusion is somewhat lower than tricresyl phosphate and Santicizer 160. It does, how--: ever, fuse more rapidly than DOP or DIDP, The water extraction of Flexol 77-0 is higher than Santicizer 160 but it is not as sensitive to soapy water extraction. It is inferior to DIDP in both afore mentioned extraction properties. '' * 7. From kerosene extraction results over a range of tempera tures it was shown conclusively that DIDP is Inferior to to DOP in this respect. 8. In the study of secondary plasticizers it was shown that, although the Aroclors are more compatible and flame retardant than the competitive chlorinated paraffins, they are nevertheless more water and soapy water sensitive. They (Aroclors) also suffer, to some extent, from poorei volatility and vapor toxicity. 9* The use of :JV r9 (2-hydroxy-4-methoxy benzophenone) with Santcwhite powder has produced the best light stability yet encoun tered in film containing appreciable amounts of H3-20. Also capable of imparting light resistance to K3-20 are mixtures of TV -$ and phenyl salicylate with bar. towhite powder. 10. Santicizer 212 (Santicizer JOG distillate) exhibited interesting plasticization properties as a secondary plasticizer but snowed poor compatibility-stability by the "window exposure test. This product is contingent upon the success of Santicizer (500 which has not been encouraging so application effort has been terminated. - t ? I % ' >: 11. The new charcoal purified DOP from cur Everett plant is completely equivalent to the original DOP production in plasticiza tion properties. % ft 12. The distillation of aanticizer .!. produces no apparent effect upon its plasticizing properties. 13. Topped (most volatile fraction removed) Santicizer l6o has an improved volatility from film as well as per se. f? 14. Santicizer 2!>, a bler.d of she exceptionally compatible ester Santicizer 160,.and a less compatible material,^alkyl bcnzone,4 ?is a primafry plasticizer*for polyvinyl c.u^vrmde.' Since* lt^s In'trd- ' duction tO;( the trade In 1958, it has been received with interest, ilts abilitytojimpart surface "slis:! to coated fabric, molded ' 1" 1 .........` .............. >lif<li4lit;' " DSW 620979 STLCOPCB4095007 si I fm gent vblatlU^y1 test-Was ^rrfttenl ; `toils new test involves" a higher temperature and longer aging period, than the standard A.S.T.M. activated Carbon test. 5 *f ; J| * i. ft. IV. FUTURE WORK 1. To continue the Intensive evaluation of potential explora tory plasticizers as well as competitive products. 2. To continue the study of secondary plasticizers. 3. To construct and compare modulus of elasticity vs. temperature curves of Monsanto and competitive plasticizers. 4. To study dodecyl benzene In admixture with other primary plasticizers such as DOP, DIDP and Santiclzer 141. V. PATENT STATUS No disclosures have been submitted to the Patent Department as a result of this work. 71. REFERENCES 1. L. R. Wangler, Application Work or. Present Plasticizers, Special Application Report No. 1, A Study of Santiclzer 213 In Polyvinyl Chloride. Report No. 1425 under Job No. 2-02-750.01-2595-1, February 22, 1956. 2. J. A. Cannon, Application Work or. Present Plasticizers. Under Job No. 2-02-750.01-2515 (to be Issued), " ' 3. P. B. Graham, Plasticizer Test Method Development, Part I; A Study of the Clash-Berg Torsion Test. Report No. 1^11 under Job No." 2-62-750.qI-304`4-1, '-r* c7 - 1955. 4. R. M. Parks, Screening Test or. Monsanto and Competitive ?lastlclzers-l954; The Intelslve Evaluation of Secondary plasticizers,i Including the Aroclors^ Final Report Ho. 1251 under Job No. 2-02-750.01-2121-1, May 16, 1955. 5. P. R. Graham,j Special Plasticizer Application. Report 1, Evaluation ofl HB-20 as a substitute for KB-40. , Report ; : * $ No .* 779: under| Jojc |Nof. 117t-2505, M |- DSW 620980 STLCOPCB4095008 &R. Gra Lzer * .'* 7. P. R. Graham, Final Report on the E^valuautniodn"oJfobStMab---ilizers 8* h R.*.w*nSler> Screening Tests on Monsanto and Comnetit-.ivA ? l.2fr3'S^?fj- application Report No. 1, Evaluation ?-ST^Zeii Lu? ^stlllate as a Secondary plasticizer PS> Report Mo- ^312 under Job Mo. 2-02-f50.0l-2b94-l, October 17, 1955. 9* q`ny: Hfraj?' Sgecia! Application Report No. 2 on Plasticizer ~.le3j^e.y7:T-P.u^nt Re3e^c^ Report No. 1340 under Job No. 2-02-750.01-2892, November 21, 1955. 10. Pinal Report under Job No. 2-02-750.01-5083, to be written. VII. TEST METHODS "-^r,^LtSSt.Pr^d'i1'es enPlyed lr. this study are contained in ~ ^?SdiIeSt Methods of the Plasticizer Application Laboratory". They a,e in ncs. c^ses adopted Iron standard A.S.T.M. procedure. VIII. DETAILS A. Application of Primary Plasticizers 1* fieii::ii`7ary Eval'Jaticn of the Santiclzer 600 Series yRef. 9)______ ;______ _____________________ fled as foTlows^*6 rnembers of the Santiclzer 600 series are irtentl- Santlclzer No. t fH * :: ? ^08 609 rv^p.nD DI0P,'DIDP DIDP, DBP toODP, 141 DOP, 141 DIDP, 160 D0P,t DOAi 3-601* 160 DIDP, DOA, 1:' DIDP,|DBP, DIEA. DO: 50:50 80:20 ,Discontinued 07:33 75:25 : ; 52.8:47.2 30:25-25 60 :1F m DSW 620981 STLCOPCB4095009 Thd re3uItfs'fof those plasticizers which wei^e evaluated will be found on ^iap#i|in the Appendix. t | s v f .f f * f v- ^ " \ ' - , It should lie noted that Santicizers 607 , 612 and 614 sire quite flexibilizing. Santicizer 6o6 is inefficient and hence its formulations would require less resin to produce a composition cf a certain hardness. Santicizer 6l4 has good permanence with respect to volatility.fc Santicizer 6ll and especially Santicizer 613 exhibit superior resistance to kerosene extraction. In water sensitivity, most of these plasticizers are comparable. Santi cizers 607, 612 and 6l4 exhibited preliminary indications of yielding formulations of good heat stability. 2. Comparison of Santicizer 603 to Flexol 426 Formulations containing Flexol 426 and those containing Santicizer 603 at concentrations of plasticizer of 20$, 40# and 50/6 were prepared. At all concentrations, Flexol 426 showed a slightly better flexibilizing effect. There was little or no difference between the volatilities. From the Shore hardness results. It can ' be noted that Flexol 426 is slightly more efficient as a plasticizer. At lower concentratidr.3 of plasticizer, the kerosene extractions do not differ significantly. However, at 40$ and 50^6 plasticizer, Flexol 426 is somewhat superior In this respect. There is verylittle difference between these plasticizers in respect to pro cessing characteristics and water sensitivity. In stability to heat, Flexol 426 Is superior; however, the difference i3 not as well defined in the case of stability to light. In either case (stability to heat or stability to light), the differences were more apparent in the poorer stabilizing system than in the epoxy type system. 3- Comparative Evaluation of S^o^iciz615 and DNQDP In an effort! to achieve an eii'lcient replacement for L'HODP /3I-(n-octyl, n-decyl) phthalate/ a series of combinations cf f-IDr (dlisodecyl phthalate) and DIDA (dilsodecyl adipate) were extensively tested in,direct comparison with DNODP. , *i i %4 ? t* < i [ DSW 620982 STLCOPCB4095010 s--<r--* ' Series Op&lon Plasticizer s < 410* IT G-62 Mark XI Mark XX 22 37 64 97 22 37 64 97 2 Series B: Opalon 410 100 Plasticizer Jl H) G-62 Mark XI Mark XX Blspnenol A NOTE: 64 (+ 3 PHR POS-C; 0.7' Plm DS-207) Plasticizer A = DNODP Plasticizer B = 25$ DIDP; 75% BID.-- Plasticizer C = 50$ DIDP; " -v. Pxastlcizer D - 75$ oIDP; 23^>, DIDA ^Santielzer 613) a. Compatibility Test Results h : it i , A3 predicted, the most serious drawback to the use > of, DIDA/DIDR combinations In place of .DNODP is the limited oompatl- f ^mitgrr 9tlfeiife|delbyH esters. Loop? Compatibility tests, ?v&ndow I t " exposures, cpmpatibility in Ha0 at 50C.; ooliahed plate and ' ' Padeometer jCpmiatiM.llty lists collectively show the DIDA/DID; dc ftl nP oe/p i(ffnrnnsa at- <tKib1 lkf TVJriTsB ^lUl.4. Eel t DSW 620983 STLCOPCB4095011 several deferees"offindompatibHiy. t It 'was found that compatibility is moat seriously:; Impaired, when the ;;iead-type stabilization system is used or If BlspHenol A&a|addad. The, combination of 75J6 DIDP255* DIDA (Santlcizer 615) was `shojim to be the most compatible of the series. Compatibility decreased proportionally with the in creasing concentration of DIDA. ; b. Fadeometer Light Stability As in the previous study, DIDP/DIDA mixtures are less stable to light than DNODP. The best stability was obtained from the Santlcizer 615 mixture. Poorer stability and more pro nounced tack formation were evident in the mixtures containing the high concentrations of DIDA. Bisphenol A Is detrimental to the light stability of Santlcizer 615. Fadeometer Exposure Results No. y800 Hours Exposure) No. (300 Hrs. Exposure) 1-A 2-A 3-A 4-A 5-A 6-A 7-A o-a 9-A 10-A 11-A 12-A 13-A No change l-B Spotted 2-3 Spotted, si. exud. 3-D Exuded 4-B Spotted, seriousexud. 5-B Very spotted 6-B SI. spotting 7-B SI. exudation 8-B Exuded 9-B SI. exudation * Very .spotted *; | , | * , = SI. spotted 'r Very si. exud. *' *K c.. Flastlclzlng Properties No change SI. tackiness SI. spotting, exud. Noticeable exud. SI. exudation Noticeable exud. SI. tacky SI. tacky Spotted, serious exud. '* ? | j ' The evaluation of thr- y vale -gentles (vola tility, TfC., etc.) of S-015fandSDNODF will ce found on Charts II. Ill and IV In the Appendix. ; . | _| > " 4. The Replacement of Santlcizer 601 with a DIDP/DIDA/DIOP Mixture t #' > I % ; -- f <f s I f |^ecius4 toCfthl fsu^iaLy fof ^di(h-oCtyl jL-Jeoyi) phthalate (DNODP), which is one: oft the components of Sanfc&izar 601, it was necessary tto *fihd a xegl^c Aeiit* for Santlcizer i6pl4.iIn|mo3t respects! f3*. ^'1 i >11 DSW 620984 STLCOPCB4095012 IN ,, .......... LnikOTifBS^^ . (hereafter referred to as the "new mixture" In this report)^,at plasticizer concentrations of 20j6, 305S, 40# and 50# were #iH*epared. *, -i - : 't . ' 4 r I ; At all concentrations, the new mixture was not quite as flexibilizlng as S-601. Shore hardness showed no significant difference with respect to plasticizer efficiency. There was little or no difference noted in volatility at any of the concentrations tested. There was no difference in the kerosene extractions at mo3t concentrations. The new mixture yielded formulations slightly more sensitive to water. However, it is doubtful that these differences are significant since the variations with respect to this property were slight at any given concentration of plasticizer. Santlcizer 601 was superior in stability to heat in both the lead and the "epoxy-cadmium" stabilizer systems. There has been little or no difference noted in respect to light stability in the lead system. After 600 hours in the fadeometer no difference in light stability was noted in the "epoxy-cadmium" system. Neither of these plasticizers showed satisfactory stability to light in __ _ the lead systems. ' For more specific details see Charts V, VI and VII in the Appendix.' - 5. Volatility of Butyl Decyl Phthalate vs. Competitive Products An extensive series of volatility tests were run on several laboratory prepared BDP. (butyl decyl phthalate) samples in comparison with Flexol 426 and a number of other competitive materials. The results of this Investigation follow: Material Volatile Loss*, # Run No. 1 Run No. 2 t1 BDP (comp.A-65820 & 65825 . BDP 1A-6583I) ? BDP (A-65836) BDP (A-65857) . BDP- (A-70253, distilled) , Flexol 426 PX .114 : Ela^te|c|4C-P : 4 <i J ! ' Butyl lsodecyl phthalate(BIDP) Santlcizer 603 ' ...... i 10.6 11.9 10.7 12.2 12.9 11.4 t f 14.0 20.4 f 16.5 13.7 1.7 Ir DSW 620985 if STLCOPCB4095013 1 i'iz $< #'. I 6. Comparison ofSanticlzer 141 to Ohio-Apex RS-1313 ^ ' The bulk of the work on^this project is reported In tne final report under Job No. 2-02-750.01-2616 (Ref. 2). However, additional work Included in the scope of this report has shown RS-1313 to be decidedly inferior to S-141 from the standpoint of compatibility. After.Bixweeka behind glass, RS-1313 developed serious incompatibility. It was also shown to be inferior to S-141 in light resistance. 7. Comparison of DIDA to Horton Withers' Morflex P-20 Morton Withers, in offering Morflex P-20 (unidentified) as a replacement for DIDA, have produced a product which is equiva lent to Monsanto DIDA in all properties except low temperature flexibility, where it possesses a slight advantage over DIDA. 40# P-20 40# DIDA 33-1/3# P-20 33-1/3# DIDA TfC. Volatility,# Flast. Lost Shore Hardness H20 Extraction, # Plast. Lost H20 Adsorption Kerosene Extraction, # Plast. Lost -69.0 0.07 0.64 76.7 75-5 -53.1 -49.4 8. Intensive Evaluation of Flexol 77-0 Because of Increased competition from Carbide and Carbon's plasticizer 77-G (ulpropylene glycol dibenzoate) addi tional information has been obtained on its performance. From the standpoint of c-ceasing, Flexol 77-G fuses r eadily; its rate of fusion being somewhat lower than tricresyl phosphate and Santicizer 160. It does, however, fuse moi^e readily than either DOP or DIDP. The water extraction of Flexol 77-G is higher than aanticizer 160 but it is not as sensitive to soapy water extraction. It is inferior to DIDP In both environments. ' i I i 11 (ill f s i It M I li t * S * rii r n mmmmm DSW 620986 STLCOPCB4095014 The following are , the ^water and soapy water extraction results of 40 mil* samples of KLexo3L|'t7rQ ;as compared to Santlclzer 160, DIDP and Santlclzer 606: * f j 'f Flexol 77-Q S-160 DIDP S-606 Water Extraction, $ Plasticizer Lost 0.39 0.24 0.02 0.09 Extraction by 1$ Ivory Flakes, % Plasticizer Lost 2.46 4.37 0.19 3.03 A Study of the Kerosene Extraction of DOP and DIDP Formulations A comparison of kerosene extraction properties of DOP and DIDA at various temperatures and concentrations was ur.dertaken in order to clarify tiie kerosene sensitivity of these two plasticizers. See Chart iio. IV. desalts: 3C. 23 c. 4oC. 5 0C. 33-1/3$ DOP 33-1/3$ DIDP -tC$ DOP 4C3 DIDP NOTE: 11.2$ 7 Cr b 60.6 73.7 15.6$ 72.6 76.2 7 p.7 S6-hour Immersion time 19.3$ 24.4 41.1 63.5 20.8$ 29.6 34.4 44.4 10. Extended Volatility Tests for^oth Monomeric and Polymeric Plasticizers In order to distinguish more clearly the differences in volatility of monomeric and polymeric plasticizers, a more stringent activated carbon volatility test was designed; 33-1/3$ .emulations .if dl-isoaecyl phtnaiate, DOP, tricresyl phosphate, rampi.x G-50, and Santlclzer 3C0 were|tested. Most of the usual conditions for; the carbon volatility test were fulfilled, except the term of heat aging was extended to 4 days and 6 days and a higher temperaturg was used. t Plasticizer STLCOPCB4095015 > ' ........ ll. Low Temperature Properties of Plasticizers Much of the work Involved in this study will be found in Final Report No. 1315 under Job No. 2-02-750.01-3044-i (Ref. 3). Since the appearance of the above report work was started on the new Tinius Olsen torsion tester. This instrument has been found to give accurate and reproducible results for the stiffness of plasticized PVC over a wide temperature range. Hie following results were obtained for Tr and T* of DOP (50 phr) using the new Tinius Olsen tester. T4 (Temp, at which Modulus of Elasticity is 10* psi) 6C. Tf (Temp, at which Modulus of Elasticity is 1.35 x 10s psi) - 22 C. These results are identical to those published by Carbide an: Chemicals Corporation. ire or. 3. Application of Secondary Plasticizers 1. Intensive Comparison of Aroclors to Competitive Chlorinated Paraffins. This study is a continuation of the work previously reported In Final Report Ho. 12-31 under Job No. 2-02-750.01-2821-1, Hay 16, 1955 (Ref. ;? 4). Monsanto's participation in the secondary plasticizer market could be improved if a niche for the Aroclors (chlorinated ' Phenyls) could be found. An intensive study of the Aroclors vs. cne chlorinated paraffins, their natural competitors, was therefore undertaken. Recent tests indicate that the Aroclors were none flame retardant and more extractable by soapy water chan the chlorinated paraffins. Evcraction studies in alkali solution indicate that there was a reaction between the NaOH and che chlorinated secondaries rather than an extraction. * * t * if-# .. and *12o0 ter be eqi^ly extraction resuj.tsj ^ho&ed Aroclors. 125^ > t ntr to Chlcrowax 70 and Pa .aflex Bh'-l (alkylated naphfchailenes) however, all of the Aroclors were worse. than tj :jl<'inated, paraffin I i DSW 620987.01 STLCOPCB4095016 I -f f i TABLE I I# Plasticizers Soapy Water Extraction* Flame-Out Time Aroclor 1232 Aroclor 1242 Aroclor 1248 Aroclor 1254 Aroclor I260 Clorafln 40 Clorafln 40V Clorafln 42 Clorafln 42S Chlorowax 40 Chlorowax 70 Halowax 4004 Panaflex BN-1 1:5 D0P) 1:5 D0P) 1 =5 D0P) 1:5 D0P) 1:5 D0P) 1:5 DOP) 1:5 D0P) 1 =5 DOP) 1:5 DOP) 1:5. DOP) 1:5 DO?) L 1 : 5 DOP) 1:5 DOP) 4.6 4.0 3.7 3.6 3-5 1.7 1.6 1.7 2.0 2.5 3.5 1.6 3.6 31 sec. 41 sec. 34 sec. 48 sec. 48 sec. 60 sec. 67 sec. 66 sec. 40 sec. 60 sec. 51 sec. 97 sec. 75 sec. * ^ plasticizer lost in l^o Ivory soap solution. Flammability tests to determine flame-out tints (General Cable Test) indicated that the Arcclcrs were more flame- retardant than the other secondaries tested except Clorafln 425. Chlorowax 70 and Panaflex BM-1 burned until they were completely charred. Extraction tests ir. yZ:/j alkali solution gave results that varied from 0.21 g. lost to C.21 g. gained, indicating that rather than extraction a chemical reaction of the secondary with NaOH occurred. * 2. Light Stability of H3-20 Several stabilization systems comprising ultraviolet Absorber No. 9> Santcwhlfe Powder mixtures, phenyl salicylate and :V 9 alone have produced the beet light stability yet encoun tered in film containing appreciable amounts of HB-20.. See Cha?*t VTII in the''Appendix. ' I H "Fof further information on the light stability of IB-20, see the, following reports: { jPin^L # 7*|^ j^d4*l$ob lfo:. 12.7~i2595 '(Ref. ^ 514 $ f f ' Final. Report ."No, 10o-" .under Job Nc. 117-2616 (Ref. 7 6)1 ' u'inal j&port ii;6 ISOMunder. Job ,Io. 2-02r750.01-2S46rI ftRe` tlj 7) l DSW 620988 STLCOPCB4095017 Evaluation of Santlclzer 2l2 4 t >" ; 1 ], )., ' ^ V' 'Jt' A Special Report has been Written concerning the per- > formance of the Santlclzer 300 distillate as a secondary-type plas ticizer for PVC. This Is Pinal Report No. 1312 under Job No. 2-02-750.01-2894-1 (Ref. #8). f The continued Intensive evaluation of Santlclzer 212 (Santlclzer 300 topped distillate) indicates It is more sensitive to soapy water than Is DOP. Prom tensile strength, elongation, and modulus determinations. It was shown that S-212 is very similar to DOP. Stabilization of S-212 has not been too successful to date. The usual stabilization systems have only prolonged com patibility from 50$ to 100^6 and poor compatibility stability is evident with two of the four stabilizer systems used. Santlclzer 212 Soapy H20 Extraction Results (15? Ivory Soap Soln., Jo hrs. at 50C.) $ Loss DOP ' S-212 (1:1 DOP) 3-212 (1:2 DC?) 3.4?6 5.3 5.4 Physical Properties of 3-212 Formulations Tensile Strength (psl) Modulus(100#) Elongatlon()6) DOP 3-212 (1:1 DOP) 3-212 (1:2 DOP) 3-212 (1:3 DOP) 2552 2532 2540 2540 1376 1296 1324 1308 391 435 415 394 H* hfi'c: ,3 to stabilize Sar.tlcizer 212 to light have not been coo sue cess Dal at the present time. In outdoor exposures the leatl i > s"3tem starred to degrade after 2 months. In. the window exposure ,,ects, t-.e lean and Stayclr. I system were, compatible after 3lx rn.0r.th3; however, the "epoxy cadmium/' and dibutyl tin dilaurate systems were incompatible after five norths. - The unstabilized I , ; fo emulations showed no signs of incompatibility for three tc I months.. ; f $ | | % f i ** I $ s f lifl | ft' f " * 1 ! ' if -- m DSW 620989 STLCOPCB4095018 HP* v&F'-Q In an effort to determine the effects of dlstlllation upon the plasticizing properties of Santicizer 1^0, a com parative evaluation of S-loO was accomplished. Screening results were very closely paralleled, showing no deviations whatever, including volatility and soapy water extraction. See Chart IX in the Appendix. Topped Topped (most volatile fraction removed) Santicizer loO is improved in volatility both per se and in PVC at a concentration. These results are foundTn Chart "IIs in the4 Appendix. D. Intensive Evaluation of Santicizer 213 Tr.e early woia. on Santicizer 215 (S-I60/DDB, 5`-l) is con tained in Final Report Mo. 1425 under Job No. 2-02-750.OI-2890-I STLCOPCB4095019 rm i t% i r: v v Both heat and light stability tests Indicate S-213;? to be : slightly inferior in comparison to 50-B. Tills inferiority'was \ more pronounced in the heat tests than in the light'tests. S-213 was shown to have a compatibility rating definitely superior to that of 50-B, which Is an accepted primary plasticizer. Two weeks in the Loop Compatibility test gave very slight indica tions of incompatibility, with the signs of exudation being more pronounced in the case of 50-B. Unstabilized S-213 exposed tc sunlight behind glass is still compatible after 3 months. Elastex 50-B developed slight tackiness after one week. Plastlsol evaluations of S-213 in an unstabilized formula tion Indicate this to be lt3 most promising field. At 80 PHR, it shows excellent viscosity-stability after one month at room temperature. Its stability is similar to DOP at 40C., in that it gels after 7 day3. Past gellation was evident at 50C. -- it gelled within one day. Santicizer 213 was tested in dry blending and extrusion as 50 PHR formulations. Faster fusion than S-160 or DOP was evi denced by shorter drying time and decreased extrusion rate. Substitution of S-213 for one fourth, of the DOP in one formulation had the effect of increasing tue drying and fusion rates. This formulation was also characterized by the "slip" quality of S-213. This Increase in fusibility and surface "slip" were noted when 3-213 was field tested at Sinclair and Rush, Inc. On the basis of tests at Weymouth Art Leather Co., the performance of Santicizer 213 was essentially equivalent to that of DOP with the exception of volatility which is noticeably poorer than that of the control. The phenomenon of surface "slip" previously noted in the use of Santicizer 213 in dip molding formulations is also evident In cloth coatings prepared from this plasticizer. This property was considered desirable by Weymouth because, at the present tine, additi-;.a! top coats are applied to surfaces having high "drag" to facilitate slipping. : Also worthy of comment was the decidedisuperiority of 3,-213 from ,the standpoint of viscosity. Testslat.Weymouth show , 3-21J i&OTlfieci f>lefetl:s5ls! to be about half* as vl^cdtis fas *disper4 * sion3 containing DOP. -;It| is conceivable that the use ?of this ; material^ might diminish the amount of diluent required or ever. ndnapkcases DSW 620991 STLCOPCB4095020 | V 1 il w iki Geon'121 DOP > S-213 DIDP Ferro 1203X Apco Thinner Rex Orange (Imperial Pigment) Formulations 2 TOT TOT 60 _ _ - -- 60 --- 0c. _______ 2 55 20 20 3 TOT __-- 30 30 2 5 20 Flexibility* (Clark) mm Abrasion Resistance Thickness, mils Spew Test, 1 hr. Results 123 46 49 55 No difference betweer 18 17 21 N.T . N.T. N.l * The lower the value, the higher the flexibility ** N.T. = No tack APPENDIX - I Notebook Pages 53744 58975 58976 59918 59922 59926 59927 59930 59945 59347 59950 64603 64604 64605 64606 64607 64613 64622 64627 64628 64629 64630 64641 6464-':- 64645 64645 64647 64648 64649 64650 66753 66754 66755 66757 66 / s8 66763 oofy. 66800 68867 68869 68870 68871 71251 71252 71270 71271 71272 71273 71274 712/5 7127b 71277 71289 72264 72265 72266 72267 72263 72269 72270 74908 7iineo 74911 74912 74913 f fr = f * f tit i ; ' ; P. R. Graham t * M tj t i Lv JJiW -W lWUJl1 STLCOPCB4095021 STLCOPCB4095022 STLCOPCB4095023 PROPERTIES OP PLASTICIZED OPALON 300 '<*** STLCOPCB4095024 STLCOPCB4095026 STLCOPCB4095027 STLCOPCB4095030 STLCOPCB4095031 I I it;'"; - *=*4 - ~ ^fCIIART IX I COMPARISON OF THE PROPERTIES OF STANDARD SANTICIZER 160 AND DISTILLED S-160 Milling Results Fuming Odor Color Distilled S-160 Mod. - heavy Mod. V. 1,. cllov; >id O " 1,-0 Mod. - heavy Modi. V. 1;. allow Molded Slicet Trane;.are;.O' OdoiColor TfC. Volatility, ; i l,.st. Lost Hardness ^ fBefore Vol. ; J `f y After Vol. Heat Stability :Color Rating II20 Extraction, \i Sol. Matl. il20 Absorption Kerosene Ex tree tion ' j. t Soapy H20 Extra otlon C1 e'. , Sli ;:.t Lt. yellow _ n .* 0 ^^ 10.,;: y 0 Ye 11 o'.; Good . c, *. 0. pvh 3 b.-> IT- ' Clea: Slight Lt. yellow _ O L- y ; 0^ 72 72 Yellow Good 3 0 [`j ^ jj,> ^.3,3 1. ly 1 mi f| M | M M j - ii 6 h it.: *1 ; Fr [P: kt- r. i DSW 621003 STLCOPCB4095032 STLCOPCB4095033