Document VG3MDjGm84vMMokkXg88vvaxq
St. Louie Research Report No. 1660 October 26, 1956
FINAL REPORT ON
APPLICATION WORK ON PRESENT PLASTICIZERS, 1955 PART II
Job Ho. 2-02-750.01-2396-11
Monsanto Chemical Company Organic Chemicals Division
St. Louis Research Department
Work<Sone by:
J. R. Darby W. G. Allen J. A. Cannon A. Y. Coran P, R. Graham L. R. Wangler
Written by:
P. R. Graham 0690606
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DISTRIBUTION
1. Pile 2. J. R. Darby J. J. H. Lum - F. B. Zienty - Pile k. Duplicate Pile 5>. Circulate: Assist, and Assoc. Research Directors 6. P. R. Graham 7. W. B. Hicks 8. H. I. Armstrong 9. H. W. Mohrman - Springfield 10. Extra 11. Extra 12. Extra
7hl3 report contalr.3 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 custody of the report which must be returned on demand.
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Page No
I. INTRODUCTION..................................................................................... 1
II. SUMMARY..................................................................................................... 1,2
III. CONCLUSIONS.......................................................................................... 2,}, 4
IV. FUTURE WORK..........................................................................................4
V. FATENT STATUS......................................................................................4
/I. RmFERlNC*S ..................... *i i
VII. TEST METHODS..................................................................................... 5
VIII. DETAILS ...................................................................................................
A. Application of Primary Plasticizers
1. Preliminary Evaluation cf the Santlcizer 600 Series ....................................................................... 3,6
2. Comparison of Santlcizer GO} to Flexol 426 . 6 }. Comparative Evaluation of Santlcizer 615 and
DUODP....................................................................................... 6,7,3 4. Replacement of S-GC1 wit:-, a DIDP/DIDA/DIOP
Mixture................................................................................ 3,9 3. Volatility of Butyl Decyl Phthalate vs.
Competitive Products ................................................. 9 6. Comparison of Santlcizer 141 to Ohio-Apex
R3-1315................................................................................10 7. Comparison of DIDA to Morton Withers'
Morflex P-20...................................................................10 3. Intensive Evaluation cf Flexol 77-0.......................... 10,11 9. A Study of Kerosene Extraction of DOP and
DIDP Formulations..........................................................II 10. Extended Volatility Tests for Beth Monomeric
and Polymeric Plasticizers .................................... 11 11. Low Temperature Properties of Plasticizers . 12
B. Application cf Secondary Plasticizers ..................
1. Intensive Comparison of Arcclor3 to Competi tive Chlorinated Paraffins ................................... 12,1}
2. Light Stability cf HB-20........................................ 1} }. Evaluation of Santlcizer 212............................... 14
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Pac** No.
C. Evaluation of Hew Process Plasticizers ...................
1. New-ProcesB DOP from Everett Plant...................15 2. New-Process Santlcizer 160 ..................................... 15
D. Intensive Evaluation of Santlcizer 213 ................... 15,16,17
APPENDIX - I ................................................................................................
Notebook Pages.........................................................................
17
APPENDIX -II ................................................................................................
Curves and Charts (See end of report) ................................
Chart No.
I Properties of Plasticized Opalon 300 Containing the Santlcizer 600 Series
II Properties of Tlastlcizers
III Volatility Per Se:S-l-0 (lorped) vs. S-160 (Standard) IV Kerosene ExtracFTon:D0P vs. DIDP V Properties of Plasticized Opalon 300 VI Evaluation of Santlcizer C-Ol
VII Evaluation of Santlcizer 6ol VIII Light Stability of HB-20
IX Comparison of the Properties of Standard Santlcizer 160 and Distilled S-l60
X Properties of Plasticized and Opalon 410 Containing Santlcizer 213
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I. INTRODUCTION
When a Plasticizer Application Laboratory, such as ours, is responsible for the company-wide testing of exploratory and commer cial organic compounds as potential plasticizers, e. well defined screening system must be employed. The first phase of this opera tion is the prcliirj.nary evaluation, to which every compound is initially subjected. Upon occasion, promising compounds emerge frc.n 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 plastisols, vinyl foam, electricals, otc. 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 1?53 and is Included as Part II cn Pinal Report No. 1J11 under Job No. 2-02-750.01-2896-1. (Ref. Mo. 1)
Prom time to tine, the Sales Department has been given tnie application data to furnish them with valuable technical informa tion 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 A. Lntenslve Evaluation of Santlcizer 213
The work on primary plasticizers includes an evaluation of the pnysical properties of a large number of the mixed plasticizers comprising the Santlcizer 600 series. In some cases, a specific member of this series is compared directly to its closest competi tor in the trade. Also Included In this category is the work Involved in finding a replacement for DflODP /dl(n-octyl, n-decyl) Phthalate7 which became scarce due to a restricted alcohol supply. Other studies on primary plasticizers reported herein are: the comparison of DIDA to its competitor Morflex P-20; an intensive evaluation of Flexol 77G (dlpropylene glycol dlbenzoate) - competi tor for Santlcizer 160; permanence properties of a number of plas ticizers; and a fundamental study of the low temperature characteris tics of plasticizers.
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Although much of the work on secondary plasticisers was reported In an earlier report (Ref. 4), additional information was obtained In 1955. This Includes a comparison of the Aroclcrs to competitive chlorinated paraffins, light stability work on HD-20, and an evaluation of Santlclzer 212.
Application information pertinent to our plant processes are al30 Included for the charcoal treatment of DOP at Everett and the laboratory distillation and topping of Santlclzer 160.
Additional application Information on Santlclzer 215 and oummary of Its properties complete the final section of this report.
The original work on floor tile evaluation was Included under tills Job number, however, the Importance of the work warranted Its separation under a separate Job number (Ref. 10).
III. CONCLUSIONS
1. Santlclzer 603 (DIDP/DBP SC:20) Is equivalent to Flcxci 426 (Carbide's butyl octyl phthalate) in all properties except light stability wnere Flexol 426 Is superior. These two products are direct competitors in the trade.
2. Santlclzer 615 (DIDP/DIDA 3:1) is the only mixed plasticizer found which compares in plasticization properties to KIODP. However, this mixture and all DIDP-DIDA combinations have lower compatibility llsit3 than Dt.'ODP. This relative Incompatibility poses a problem in its usage and Indicates that caution must be used during formulation.
3. A mixture comprising 37.5$ DID?, 12.5$ DIOP, 50$ DIDA may be used as a replacement for Santlclzer 01 (Df.'CDP/DIOP 1:1) lr. applications where S-601 was recommended. When using thl3 mixture most properties are equivalent, however, a slight sacrifice In lev; temperature flexibility, water resistance and heat stability must be expected.
4. Ohlo-Apex plasticizer RS-1313 (probably a mixture of tricresyl phosphate with a fatty acid e3ter like butyl oleate) is definitely less compatible than Santlclzer 141. Moreover, the competitive mixture is decidedly less light stable than 3-141. This discovery has definitely stopped the early competition en countered with RS-1313 in flame resistant formulations.
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5. Morflex P-20 (Horton Withers' unidentified low temperature plasticizer) is completely e<]ulvalent in properties to DIDA. It is, in fact, slightly superior in low temperature flexibility.
6. Plexol 77-0 fuses readily, its rate of fusion is somewhat lower than tricresyl phosphate and Santlolzer 160. It does, how ever, fuse more rapidly than DOF or DIDP. The water extraction of Flexol 77-0 is higher than Santlclzer 160 but it is not as sensitive
to soapy water extraction. It is inferior to DIDP in both afore mentioned extraction properties.
7. Prom 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 poorer volatility and vapor toxicity.
9. The use of UV >*9 (2-hydroxy-4-methoxy benzophenone) with Santowhlte powder has produced the best light stability yet encoun tered in film containing appreciable amounts of KB-20. Also
capable of Imparting light resistance to HB-20 are mixtures of
UV *9 and phenyl salicylate with Santowhlte powder.
10. Santiclzer 212 (Santlclzer 300 distillate) exhibited interesting plasticization properties as a secondary plasticizer but showed poor compatibility-stability by the vlndow exposure test.
This product is contingent upon the success of Santlclzer 300 which has not been encouraging so application effort has been terminated.
11. The new charcoal purified DOP from our Everett plant is completely equivalent to the original DOP production in plasticiza tion properties.
12. The distillation of Santlclzer 160 produces no apparent effect upon its plasticizing properties.
13. Topped (most volatile fraction removed) Santlclzer 160 has an Improved volatility from film as well as per se.
14. Santlclzer 213, a blend of the exceptionally compatible ester Santlclzer 160, and a less compatible material, alkyl benzene, is a primary plasticizer for polyvinyl chloride. Since its intro
duction to the trade in 1956, it has been received with interest.
Its ability to impart surface "slip" to coated fabric, molded articles and transparent boats has been responsible for the
enthusiasm shown for t.nis product. 0690612
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15. In order to distinguish more clearly the differences in volatility of monomeric and polymeric plasticizers, a more strin gent volatility test was written. This new test involves a higher temperature and longer aging period than the standard A.3.T.M. activated carbon test.
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.
5. 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, DXDP and Santlcizer 141.
V. PATENT STATUS
No disclosures have beer, submitted to the Patent Department as a result of this work.
VI. REFERENCES
1. L. R. Mangier, Application Work on Present Plasticizers. Special Application Report Ho. 1. A Study or Santlcizer 213 in Polyvinyl Chloride. Report No. 1425 under Job No. 5^-750701-2#b-l, FeFniary 22, 1956.
2. J. A. Cannon, Application Work or. Present Plasticizers. Under Job No. 2-02-?50.Ol-26'lb ito be Issued).
3. P. B. Oraham, Plab;lcizer Test Method Development, Part I; A Study of the~Clash-^erg Torsion Test. Report ho. 1311 under Job Ho. 2-02-750.iiI-3044-l, September 27, 1955.
4. R. M. Parks, Screening Test on I!sr.3anto and Competitive Plasticlzers-1^54: The Ir.telslve valuation of Seiondary Plasticizers, Including tne Aroclors. Pinal Report No. I5BTunder ToV Ho. i-62-75S-.'fil,-,2i5T-I, May 16, 1955.
5. P. R. Graham, Special Plasticizer Application Report 1, Evaluation of HB-20 as a Substitute for HB-40. Report Ho. 779 under Job Ho. 117-2595, September 23, 1953.
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6. P. R. Graham, Special Plasticizer Application Report No. 2 on The Evaluation or HB-20 as a substitute tor hS-40. Report Ho.' 1385 under~Job~W: llT->lb'-Tr;~Ju'Iy
7. P. R. Orahara, Pinal Report on the Evaluation of Stabilizers for Polyvinyl Chloride. Report No. 1504 under Job No. S=S5=750T=29TCTW*. 1956.
8. L. R. Mangier, Screening Testa on Monsanto and Competitive Plastlcl2ers-Special Application Report fJo. l. Evaluation of Santiclzer yd Pistillate as a Secondary Plasticizer for Pol.vvinyl Chloride. Report Ho. 1312 under Job No. 2-53-75. Ol-lBSW-I/' '6c' tober 17, 1955.
9. A. y. Coran, Special Application Report No. 2 on Plastic!ter Sales Development Resea: ch. Report No. 1340 under Job ho. November 21, 1955.
10. Pinal Report under Job Ko. 2-02-750.01-508?, to be written.
VII. TEST METHODS
The test procedures employed In this study are contained In "Standard Test Methods of the Plasticizer Application Laboratory". They are In most cases adopted from standard A.S.T.M. procedure.
VIII. DETAILS
A. Application of Primary Plasticizers
1. Preliminary Evaluation of the Santiclzer 600 Series
(P.ef. 9)_________________
__________________________
The members of the Santiclzer 600 series are Identi fied as follows:
Santiclzer No.
601 602 60? (604 (|05 606 607 608
609 610 611 612 613 614 615
EhODP, DIOP DIOP, DIDP DIDP, DBP DnODP, 141
DOP, 141 DIDP, 160 DOP, DOA
S-601, 160 DIDP, DOA, loO DIDP, DBP, DIDA DIDP, 160 DOP, DOA DIDP, 160 DIDA, DIDP DIDP, DIDA
50:50 50:50 80:20
6677::333?))TMW8.,
67:33 75:25 52.8:47.2 50:25:25 60:15:25 50:50 59-5:40.5 33:67 50:50 75:25
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The results of those plasticizers which were evaluated will be found on Chart I in the Appendix.
It should be noted that Santioizers 607, 612 and 614 are quite flexlbilizing. Santlcizer 606 is inefficient and hence its formulations would require less roain to produce a composition cf a certain hardness. Santlcizer 614 has good permanence with respect to volatility, Santlcizer 611 and especially Santlcizer 613 exhibit superior resistance to kerosene extraction. In water sensitivity, most of these plasticizers are comparable. Santlclzers 607, 612 and 6l4 exhibited preliminary indications of yielding formulations of good heat stability.
2. Comparison of Santlcizer 603 to Flexol 426
Formulations containing Flexol 426 and those containing Santlcizer 603 at concentrations of plasticizer of 20}S, }o, 40Jt and 50% were prepared.
At all concentrations, Flexol 426 showed a slightly better flexlbilizing 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 concentrations of plasticizer, the kerosene extractions do not differ significantly. However, at 40$ and 50$ plasticizer, Flexol 426 is somewhat superior in this respect. There is very little difference between these plasticizers in respect to pro cessing characteristics and water sensitivity.
In stability to heat, Flexol 426 is superior; however, the difference is 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 Santlcizer 615 and DtTODP
In an effort to achieve an efficient replacement for DNODP /3i-(n-octyl, n-decyl) phthalate^ a series of combinations of DIDF (dllsodecyl phthalate) and DWA (dllsodecyl adipate) were extensively tested in direct comparison with DtlODP.
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Formulations
Serlss At Ogalon
Plastlclzer A C TT 0-62 Mark XI Mark XX
1 100
64
2m
22
ft
l it
ll
22 fl N fl
1
n
II M
n 97
ft ft
n 22
tt
In
57 11
64
fl
ft
x9o it
II ft 12 tt 15 n
97
22
57
64
97
ft
fl ft
ft fl
ft
ft
II II
ft
Ssrlss B:
Plasticizer _k
0-62 Mark XI Marie XX Blsphenol A
\1
2
l
l 9
10m0 m it ti
ft
n
n
n
64 64
l
2
ft
1fl
64 ft fl
fl
64 64 64 64 64
It
It
ft
ft
ft
ft
ft
ft
ft
II
fl ft ft ft ft
64 (+ 3 PHR POS-C; 0.75 PHR DS-207)
0.1
0.5 o.l 0.5 o.l 0.5 0.1
0.5 0.5
DOTE: '
Plasticizer A - DNODP Plasticizer B - 2555 DIDP; 75% DIDA Plasticizer C - 50% DIDP; 50% DIDA Plastlclzer D - 75% DIDP; 25% DIDA (Santlelzer 615)
a. Compatibility Test Results
As predlcted, the most serious drawback to the use of DIDA/DIDP combinations In place of DHODP Is the limited compati bility of the laodecyl esters. Loop compatibility tests, window exposures, compatibility In H0 at 50*C., polished plate and Fadeometer compatibility lists collectively show the DIDA/DIDP combinations to be less compatible than DNODP. Various plasticizer concentrations (stabilized with a series of systems) displayed
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0I
several degrees of incompatibility. It was found that compatibility Is most seriously Impaired when the lead-type stabilization system Is used or if Blsphenol A Is added. The combination of 7556 DIDP-
25$ DIDA (Santlcizer 615) was shown 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 ere less stable to light than ENODP. The best stability was obtained
from the Santiclzer 615 mixture. Poorer stability and more pro nounced tack formation were evident in the mixtures containing the high concentrations of DIDA. Blsphenol A is detrimental to the light stability of Santlcizer 615.
Fadeometer Exposure Rosults
Mo.
1-A 2-A ?-A 4-A 5-A 6-A I-A o-A 9-A 10-A 11-A 12-A 13-A
(800 Hours Exposure)
Wo.
No change Spotted Spotted, si. exud. Exuded Spotted, serious exud.
Very spotted SI. spotting
SI. exudation
Exuded SI. exudation
Very spotted SI. spotted
Very si. exud.
1-B 2-3 3-B 4-B 5-B 6-B
T-B S-B 9-B
(300 Mrs. Exposure)
No change SI. tackiness SI. spotting, exud. Noticeable exud. SI. exudation Noticeable exud. SI. tacky SI. tacky Spotted, serious exud.
c.. Plasticizing Properties
The evaluation of the physical properties (vola tility, Tf*C., etc.) of S-6l5 and MiODP will be found on Charts II, III and IV in the Appendix.
4. The Replacement of Santlcizer 601 with a DIDP/DIDA/DIOP Mixture
Because of the dwindling supply of dl(n-octyl,n-decyl) phthalate (DfJODP), which is one of the components of Santlcizer 601, It vras necessary to find a replacement for Santlcizer 601. In most respects, a mixture of DIDP, DIDA and DIOP, 375sl2.5:50 Is very similar to Santlcizer 601. Though the new mixture exhibits less stability to heat In Its formulation, the stability to light appears to be comparable.
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9.
Formulations containing Santlclzer 601 (CNODP and DIOP, 50:50) and those containing a mixture of DIDP, DIDA and DIOP, 37.5*12.5*50 (hereafter referred to as the "new mixture" In this report) at plasticiser concentrations of 20$, 50$, 40$ and 50$ were prepared.
At all concentrations, the new mixture was not quite as flexlblllzlng 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
tected. There was no difference In the kerosene extractions at most 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.
Santlclzer 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
tne lead systems.
For more specific details see Charts V, VI and VIZ 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 Hun uo. "i
BDP corap.A-65820 It 65825) BDP A-6583I) BDP A-65O36) BDP A-65837) BDP A-70253, distilled) Flexol 426 PX 114 Elastex 40-P Butyl isodecyl phthalate(BIDP)
Santlclzer 603 DOP Santlclzer 160
10.9 11.4
10.9 11.6 11.0
9.9 11.9 16.9 14.0 12.2
4.3 10.1
10.6
11*9 10.7 12.2 12.9 11.4 14.0 20.4
16.3 13.7
5.7 11.3
* Te3t specimens for runs the same milled sheets.
1 and 2 were taken from 0690618
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6. Comparison of Santlclzer 141 to Ohlo-Apex RS-1313
The bulk of the work on this project Is reported In the final report under Job No. 2-02-750.01-2616 {Ref. 2). However, additional work Included In the scope of this report has shown
7S-1313 to be decidedly Inferior to S-141 from the standpoint of
compatibility. After six weeks behind glass, RS-1313 developed serious Incompatibility. It was also shown to be Inferior to S-141 In light resistance.
7. Comparison of MPA 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.
*0* P-20 40* DIDA 33-1/3* P-20
Tf*C.
Volatility, Plast. Lost
Shore Hardness H20 Extraction, *
Plast. Lost H*0 Adsorption Kerosene Extraction,
* Plast. Lost
-69.0
*5 73
0.07 0.64
76.7
-65.3
4.7 77
0.07 0.55
75.5
-53.1
-49.4
8. Intensive Evaluation of Flexol 77-0
Because of increased competition from Carbide and Carbon's plasticizer 77-0 (dlpropylene glycol dlbenzoate) addi tional Information has been obtained on its performance. From the standpoint of processing, Flexol 77-0 fuses readily; Its rate of fusion being somewhat lower than trlcresyl phosphate and Santiclzer I 160. It does, however, fuse more readily than either DOP or DXDF.
The water extraction of Flexol 77-0 Is higher than Santiclzer 160 but It Is not as sensitive to soapy water extraction. It Is Inferior to DIDP In both environments.
\
HARTOLDMONOOQ5179
11
The following are the water and soapy water extraction results of 40 mil samples of Flexol 77-0 as compared to Santlcizer
l6o, DIDP and Santlclser 606:
Flexol 77-0 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
9. A Study of the Kerosene Extraction of OOP and DIDP Pormulatlons
A comparison of kerosene extraction properties of OOP and DXDA at various temperatures and concentrations was under
taken In order to clarify the kerosene sensitivity of these two plasticizers. See Chart tlo. IV.
Results;
23 *C.
40 C.
50*C.
33-1/3* DOP
33-1/3* DIDP 40* DOP 40* DIDP
11.2* 76.6 60.6
73.7
15.6* 72.6 76.2 75.7
19.3* 24.4 41.1
63.5
20.8* 29.6 34.4 44.4
NOTE: S6-hour Immersion tine
10. Extended Volatility Tests for both 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*
formulations of di-lsodecyl phthalate, DOP, tricresyl phosphate,
Paraplex 0-50, and Santlcizer 300 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 temperature was used.
Plasticizer 1-Day Vest./'C.
* Plasticizer Loss o-Day !fest,5f7vc. 4-Day Test,l05"C
DOP 4.5 -- 45.4
TCP 1.0
6.7
24.3
DIDP
1.6
5.6
13.2
0-50
1.3
--
3.0
S-300
1.1
3.5
7.0
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HARTOLDMONOOQ5180
12
11. Low Temperature Properties of Plasticizers
Much of the work Involved In this study will be found In Pinal Report No. 1515 under Job No. 2-02-750.01-5044-1 (Rof. 5).
Since the appearance of the above report work was ctarted on the new Tlnlus Olsen torsion tester. Tills Instrument
has been found to give accurate and reproducible results for the stiffness of plasticized PVC over a wide temperature range.
Ine following results were obtained for Tf and T of OOP (50 phr) using the new Tlnlus Olsen tester.
T (Temp, at which Modulus of Elasticity Is 10* psl)
+ 6*C.
Tf (Temp, at Which Modulus of Elasticity is 1.J5 x 10 poi)
-22*C.
These results are identical to those published by Carbide and Carbon Chemicals Corporation.
B. Application of Secondary Plasticizers
1. Intensive Comparison of Aroclors to Competitive Chlorinated Paraffins
This study Is a continuation of the work previously reported In Pinal Report llo. 1281 under Job No. 2-02-750.01-2321-1,
May 16, 1955 (Ref. 4).
Monsanto's participation in the secondary plasticizer market could be Improved If a niche for the Aroclors (chlorinated
biphenyls) could be found. An Intensive study of the Aroclors vs. the chlorinated paraffins, their natural competitors, was therefore undertaken. Recent tests Indicate that the Aroclors were more flame retardant and more extractable by soapy water than the chlorinated paraffins. Extraction studies In alkali solution Indicate that there was a reaction between the NaOH and the chlorinated secondaries rather than an extraction.
Soapy water extraction results showed Aroclors 1254 and 1260 to be equivalent to Chlorowax 70 and Panaflex BN-1 (alkylated naphthalenes), however, all of the Aroclors were worse than the other chlorinated paraffins.
0690621
HARTOLDMONOOQ5181
13.
TABLE I
Plasticizers
Soapy Water Extraction* Flame- Oat Time
Aroclor 1232 i 5 DGP] Aroclor 1242 i 5 DOP Aroclor i248 i 5 DOP Aroclor 1254 i 5 DOP Aroclor 1260 i 5 DOP Clorafln 40 i 5 DOP Clorafln 40V i 5 DOP Clorafln 42 i 5 DOP Clorafln 423 i 5 DOP Chlorowax 40 i 5 DOP Chlorowax 70 i 5 DO? Halowax 4004 i 5 DOP i Panaf**lex BN-1 [i 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.
sec* (>6 sec* 40 sec. 60 sec. 51 sec. 97 sec. 75 sec.
* ? plasticizer lost In 1J< Ivory soap solution.
Flammability tests to determine flame-out times (Oeneral Cable Test) Indicated that the Aroclors were more flameretardant than the other secondaries tested except Clorafln 42S. Chlorowax 70 and Panaflex BII-1 burned until they were completely charred.
Extraction tests In 50? alkali solution gave results that varied from 0.21 g. lost to 0.21 g. gained. Indicating that rather than extraction a chemical reaction of the secondary with llaOH occurred.
2. Light Stability of HB-20
Several stabilization systems comprising ultraviolet
Absorber Ho. 9, Santowhlte Powder mixtures, phenyl salicylate and UV Ho. 9 alone have produced the best light stability yet encoun tered In film containing appreciable amounts of HB-20. See Chart VIII In the Appendix.
For further Information on the light stability of HB-20, see the following reports:
Final Report Ho.779 under Job Ho. 117-2595 (Ref. # 5) Final Report l.'o. 1005 under Job Ho. 117-2616 (Ref. # 6) Final Report Ho. 1504 under Job Ho. 2-02-750.01-2946-1 (Ref.
7)
0690622
HARTOLDMONOOQ5182
3. Evaluation of Santiclzer 212
A Special Report has been written concerning the per formance of the Santiclzer 300 distillate as a secondary-type plas ticizer for PVC. This is Pinal Report Ho. 1312 under Job Ho. 2-02-750.01-2891*-1 (Ref. # 8).
The continued intensive evaluation of Santiclzer 212 (Santiclzer 200 topped distillate) indicates it is more sensitive to soapy water than is DOP. Prom tensile strength, elongation,
and modulus determinations, it was sho'.m that S-212 is very similar to DOP. Staolllzatlon of S-212 has not been too successful to date. The usual stabilization systems have only prolonged com patibility from 50$ to 100$ and poor compatibility stability 1b
evident with two of the four stabilizer systems used.
Santiclzer 212 Soapy H0 Extraction Results
(1$ Ivory Soap Soln., 96 hrs. at 50*C.)
$ Loss
DOP S-212 (1:1 DOP) S-212 (1:2 DOP)
3.4$ 5.8 5.4
Physical Properties of S-212 Formulations
Tensile Strength (psl) Modulus(100$) Elongatlon($)
DOP S-212 (1:1 DOP) S-212 (l:2 DOP) S-212 (l:3 DOP)
2552
2532 2540 2540
1376
1296 1324 1308
$
5
Efforts to stabilize Santiclzer 212 to light have not been too successful at the present tine. In outdoor exposures the lead system started to degrade after 2 months. In the window exposure tests, the lead and Staycln I systems were compatible after six months; however, the "epoxy cadmium" and dlbutyl tin dllaurate
systems were incompatible after five months. The unstablllzed formulations showed no signs of Incompatibility for three to four
months.
0690623
HARTOLDMONOOQ5183
15.
C. Evaluation of New Process Plasticizers
1. Hew Process POP from Everett Plant
A sample of plant process HOP (di-2-ethylhexyl p.ithalate) from new Everett production was screened and found to bo completely equivalent to present production DOP. Heat and light tests emphasised this same equivalence.
Tp*C. Volatility Kerosene Extraction
DOP (Everett Composite) -38.3
DOP (Standard)
-38.2
4.6# 4.6
54.5# 49.3
2. New Process Santlclzer 160
a. Distilled S-l60
In an effort to determine the effects of distilla tion upon the plasticizing properties of Santlclzer 160, a com parative evaluation of S-160 was accomplished. Screening results were very closely paralleled, showing no deviations whatever. Including volatility and soapy water extraction. See Chert IX In
the Appendix.
b. Topped S-160
Topped (most volatile fraction removed) Santlclzer 130 Is Improved in volatility both per se and In PVC at a 40# concentration. These results are four.dTn Chart II In the
Appendix.
D. Intensive Evaluation of Santlclzer 213
The early work on Santlclzer 213 (S-16O/DD0, 3:1) Is con tained In Pinal Report Ho. 1425 under Job No. 2-02-750.OI-2C9S-I (Ref. # 9). However, at the expense of some repltltlon a summary
of the work presented up to the end of 1955 is Included here.
Santlclzer 213 was screened preliminarily at 20#, 30#, 40#
ar.d 50# concentrations In a direct comparison with Elastex 50-3 (Barrett's butyl cyclohexyl phthalate), a product of apparent similar plasticizing characteristics. This similarity was evident lr. most of the screening tests. It is, however, more water sensi tive than Is 50-B. See Chart X.
0690624
HARTOLDMONOOQ5184
16. I
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. Unstablllzed S-213 exposed to sunlight behind glass Is still compatible after 3 months. Llastex 50-B developed slight tackiness after one week.
Plastlsol evaluations of S-213 in an unstablllzed formula tion Indicate this to be Its most promising field. At 80 Pin, It shows excellent viscosity-stability after one month at room temperature. Its stability is similar to DOP at 40*C., In that It gels after 7 days. Past gellatlon was evident at 50*C. -- It gelled within one day.
Santlclzer 21? was tested in dry blending and extrusion as 50 PHR formulations. Faster fusion than S-I60 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 the drying and fusion rates. Tills formulation was also characterized by the "slip" quality of S-213. This increase In fusibility and surface "slip" were noted when S-213 was field tested at Sinclair and Rush. Inc.
On the basis of tests at Weymouth Art Leather Co., the performance of Santlclzer 213 was essentially equivalent to that of DOP with the exception of volatility which la noticeably poorer than that of the control.
The phenomenon of surface "slip" previously noted In the use of Santlclzer 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, additional top coats are applied to surfaces having high "drag" to facilitate slipping.
Also worthy of comment was the decided superiority of S-213 from the standpoint of viscosity. Tests at Weymouth show S-213 modified plastlsols to be about half as viscous as disper sions containing DOP. It Is conceivable that the use of this material might diminish the amount of diluent required or even eliminate It entirely in some cases.
0690625
HARTOLDMONOOQ5185
Coated Fabric Evaluation
Oeon 121 top
S-213 DIPP
Ferro 1203X Apco Thinner
Rex Orange (Imperial Pigment)
Formulations -r~----------- 5---------- xSs JW IOT
60 ... 60 -- - ---
30 30
222
555
20 20 20
Flexibility* (Clark) mm Abrasion Resistance
Thickness, mils Spew Test, 1 hr.
1 ------R---e--s--u--l-t-s----- Jl.
46 49 55
Ho difference between samples
18 17 21
11/P.
N.T.
N.T.**
The lower the value, the higher the flexibility
N.T. - Ho tack
APPENDIX - I
notebook Pages
527W 56975 58976 59918
59922 59926
59927 59930
59945 59947 59950 64603 64604
64605 64606
64607 64613 64622 64627 64628
64629 64630 64641 64644
64645 64646
64647 64648 64649 64650 66753 66754 66755 66757 66758 66763
I
68867
68869 68870 68871 71251 71252 71270
71271 71272 71273 71274
71275 71276 71277
71289 72264
72265 72266
72267 72268
72269 72270 74908
74909 74911 74912 74913
P. R. Grahan
r.d 5-19-57
J. R. Darby
0690626
HARTOLDMONOOQ5186
CURVES AND CHARTS
0690627
HARTOLDMONOOQ5187
0690628
HARTOLDMONOOQ5188
20* 3-615 20* OnOOP
i
30* 3-615 I 30* OnOOP
*0* S-*15 1 *0* DnODP
501! 3-515 , 50* DnODP
C HART II PROPERTIES OK PL.'.3TICIZliH3
Tf*C.
V o la tility
A fte r Vol. %S o lu b ility
Hardneas
A
t
a0.
&
Water Abaorotlon
C
HO
* e
0
9)
<
V
Kerosene _Eitiln,-.
*10.1 2.* 100 100 0.01 0.20 31. Inc. 11.2 2.8 100 00 0.00 0.23 31. Inc.
-20.5 2.7 9* 81 0.01 0.23 -25.1 2.9 58 87 0.02 0.37
30.9 22.2
-*6.3 2.1 -*6.5 2.2
76 72
70 0.02 0.52 73 0.01 o.*o
77.7 69.0
-65.0 2.5 58 53 0.0* 0.61 -63-9 2.9 61 56 0.01 0.53
R5.0 77.6 <
I
3-160, Topped
-2* .0 9.6 7* 73 0.09 0.71
3-160 (Analytically Pure) -23-T 9.7 76 71 0.09 0.7*
' !5 S-l60, Standard
-23.2 11.1 7* 73 0.09 0.66
3-3 3.5 3.6
0690629
HARTOLDMONOOQ5189
HARTOLDMONOOQ5190
J**' iC
o
o
HARTOLDMONOOQ5191
f'hsilclifr "of jnl<?ss ap^cIf led
*i r. j. TV3'-:'
I
ER.I&-. ^
-tel *
I>
PIDF
d:op
;r.*w > ; . i
"
VI*t* r. y *I . UXL
Lt.
.
vL-t. !I ilU
p.c;
Stnticizer 6C1 ??*
?0
Lt.
1*1 101
V. Lt.
ve)
-* i
c .-
c.o* * ,*Q f.C C ,0* Utt-
0690632
HARTOLDMONOOQ5192
CHART MO. VI EVAU'ATTON OP 0,\..7ICIZER 601
l o s t S X J r..
1/b/a -
fi/ity
*<? Ji?
*0
&
//c/fes- Corfc /sSJ
0690633
HARTOLDMONOOQ5193
CHART HO. VII EVALUATION OF SAl/TICT-Tl .01
/rest
i
/^/ast/C/X&r Cortc fsfJ
0690634
HARTOLDMONOOQ5194
CHART NO. VII EVALUATION OF SAKTICT-Jl vOI
Sard
/ress
JO to SO /^/aftf 'c/*^ Cone CsCJ
0690635
HARTOLDMONOOQ5195
CHART VIII LIBIff STABILITY OF HB-20
Forailatlons
' 1 2 3 4 JL 6 _L 8 JL 10 11 12 JL2_ 14
Ojwlon 300
100 100 100 100 100 100 100 100 100 109 100 100 100 100
DOF 25 53 >7.5 25 25 20 33 33 33 2U 37.5 37.5 37.5 37.5
HB-20
25 17 12.5 25 2> 25 17 17 17 17 12.5 12.5 12.5 12.5
0-60
3>3 333333 33 3 3 3
Hark XI
222 22222222 2 2 2
Hirk XX
ii1 i11 11ii1 1 1 i
Salol
4
343
4
UV No. 9 Santowhlte Powder
22
2
1
2 2
21
2 2
2
Sontlclzer 1X1
55
5
Hours Expo--d in Uoatherontter i 2 2
4
C I 8 2 1C 11
12 12
14
0
50 130 200 >00
Soo
500 wOO 700 *00 1000
000
0 0 0 0 00
00
0
0
0
4 53
20i 001
00
0
1
0
5
3
21 2 1 01
01
01
1
5 1 3 54
3 3
i 2
2 3
1 2
0 0
2 2
01 01
0 1
2 2
1 2
5 e 4
323 212
12
1
2
2
5k 4
42
21 2
12
1
2
2
5a 5.4
4 4
4 4
2 24
5 3
1 1
2 2
22 22
1
2 2
2 2
54 4
4 34 3 22
22
1
3
2
54 4
434 322
22
1
3
2
CODE
0 Colorless 1 SI. discoloration 2 Light yellow
3 Yellow 4 Light anker 5 Anker
Dark anber Brown
Black
0690636
HARTOLDMONOOQ5196
CHART IX
COMPARISON OP THE PROPERTIES OP STANDARD SANTICIZBR
luO AND DISTILLED 3-160
lulling Results
Puming Odor Color
PlBtlllod $-160
Mod. - heavy Hod. V. lt. yellow
lljldod Sheet
Transparency Odor Color Tr*C.
Volatility, 2 Float. Loot Hardness
Before Vol. After Vol. Heat Stability Color Rating Ha0 Extraction, 2 Sol. Natl. Ha0 Absorption Kerosene Ext.'action Soapy HaO Extraction
Clear Slight Lt. yellow -2yc.
10.02
/K V2
Yellou Good o.ov2 o.i>52 3 V.' 17.22
Std. S-li'O
Mod. - heavy Mod. V. lt. follow
Clear Slight Lt. yellow -23.0'C. S--YJS V2 72 Yellow Good 0.072 0.53,2 3*32 17.12
I S
i
069063?
HARTOLDMONOOQ5197
- PU
PUatlcleer 10* unite epeetfled
Bent'-clzer 213 20*
llutv DO-8 aojt
ftentlclser 213 30^
Clastcx DO-8 >0JS
Santlclzor 213 40C
Slaatox 50-B
Sontlcizer 213
Elastox 50-B . 305:
I OMIM 500
Ml mu t Tl cult
Mhoildietd
Ve-
ii
*
2
ko
s
rio9. 3
1
okO
u*koO4
Mod. Wavy Mod. Heavy
Lt. 81. Aab
T,m
Lt. SI. Aab
SI. Cl*ai Mod Y1
SI. Lt. Cl . ttod Y1
20 20
e
-*K44* #m4
5 ** *Am*.
^
Beet Be: doeie itablll
Bet r Abeoi ptlo
0 Vk0. x
HO k 5
it t
t. 0
a* noa6A0.0nm
?
*
S'* Ml
ee
a <
t d
jS *S**
5.0 LOO 100 Aab. p 0.00 0.45 1.0 Lt.
A.7 100 100 Aab. t 0.00 0.43 1.1
Mod. Lt.
SI. Lt.
ieavy SI. Aab Cleai Mod Yel - 1.7 10.2
Mod.
V.
feavy SI. DU
Mod fill
Mod.
lvy
fill
Mod.
Ieavy Str. Cl.
Mod.
Ieavy Str. Cl.
Lt. Clea: SI. Y1
V.
SI. Lt.
Cleai rtoi Yel
V.
SI. Cld7 SI. Cldy
V.
SI. Lt. ffrjl Yfl
V.
SI. Lt.
Mod Yel
'V. SI. SI. Lt. Cldy. Mod Yel
1.9 12.5 .01 .n -18.1 -17.9 _ 18.5 -52.5 17.3 -51.5 22.1
Lt. 98 97 Aab. p 0.1^ 0.79 2.1
ttc. 0 9f 99 Yel. p 0.09 0.89 1.7
Lt.
1? (ft
f 0.34 1.2? 5.2
78 W Yel. a fiifi9 0,95 5.2 71 74 Yel. 0 o.6o 1.65 10.1
Lt. GO 66 Yel. 0 0.16 1.33 9.8
0690638
HARTOLDMONOOQ5198