Document gaN0Gb1EjbOL2mzzJpvXZwbde
N42388
. I. DU PONT BE NEMOURS & COMPANY Pigments Department
SERIAL NO.j KN-69-I9
Copy No.:
/V
NEWPORT PLANT PIGMENT COLORS RESEARCH REPORT SUBJECT: 4,11-BICHLOR DQA TFA PROCESS PERIOD COVERED: OCTOBER, 1968 - SEPTEMBER, 1969
DATE: 2/17/VO
SERIAL NO.: XN-69-19
RETURN TO JACKSON LABORATORY
FILE ROOM
i
DUP050081747
XN-69-19 COPY WO.,
,1. Kmmerieal Fil.e 223.91 - Newark
2 Research Office File - Newark ** 223,91
Newark Library File - 223,91 - Newark
M, Hunt/E, Gonick - Wilmington
W, S, Struve ~ Newark
P, F, jEhrich/So F, Klenke/B,, B, Perkins - Newark
l: P, 3, Monahan {'Vital Becords) Newark W, CK Fisher Central Res. Dept, ~ Escpl. Static
it; Es L, Hodoviskas/R M, SaXemi/J, B. Lojewski Newport B, A o Johnson Newport
.IX. Ba H. Wetael/J, W, Minnieh/W0 A, West - Newport
12 J, F, Maurer
S: Newport Colors Research File (M, C. Crossan)
15.
16,
Exst ra II
S: II
NEWPORT PLANT
subj ec t ?
PIGMENT
COLOR......S
RESEARCH REPORT .............. .
4,;i i~d x c h l q h BQA TFA PROCESS
PERIOD COVERED? OCTOBER, Xg68 - SEPTEMBER, 1969
CHARGE? 4631-350-16
,
SUBMITTED Bis ft. A, JOHNSON ^ ^ ^ DATE SUBMITTED? IO/I/69
APPROVED BY? 3, F*
DATE ISSUED? 2/17/70
ABSTRACT
A TFA process, using the N-siethyl&niXIne salt as con densation catalyst, has been developed for making 4,11-ClgDQA, The unfavorable equilibrium controlling the condensation ms overcome to give good yields. Tar formation has been minimised.
RETURN TO JACKSON LABORATORY
FILE ROOM
DUP050081748
TABLE OF CONTENTS
I, INTRODUCTION AND OBJECTIVES II, SUMMARY AND CONCLUSIONS III, .PATENT STATUS IV, SUGGESTIONS FOR FUTURE WORK V, DISCUSSION OF RESULTS VI * REFERENCES
Page 1 1 2 2 2 7
DUP050081749
~ 1~
I INTRODUCTION AND OBJECTIVES
Production is currently using a PTSA process for making 4,ll-CleDQA. This process appears limited to a iOWjb concentration. At higher concentrations.,, both yield and fluorescence drops off. Even at the 108# concentration, yields are less than optimum. These yield losses contribute to the tar problem. It was the object of this study to develop a workable TPA process which would operate at increased batch con centrations, would increase yield, and would produce less tars.
II. SUMMARY AND CONCLUSIONS
1. A TPA process was developed for making 4,11-C12DQA at a 216$ batch concentration. Further increases in batch concentration should be possible.
2-. The condensation step is controlled by an unfavorable equilibrium. Water removal is the key to maximizing yield.
3. Increased condensation temperature is the least effective means of increasing yield, since it is limited by the volatility and/or dissociation of the catalyst.
4. The vapor pressure of water can be reduced to increase the condensation yield by lowering pressure either alone or 'in combination with a nitrogen sweep.
5. Conditions which are effective for reducing the vapor pressure of water also remove the self cata3.yst, the o-chloranilinium salt of TPA. This can be minimized by using a less volatile catalyst such as the N-methylanilinium salt of TFA.
6. Toe use of the N-methylanilinium salt of TPA as catalyst should eliminate plugging during its removal by distilla tion, since it is a liquid (MP 26-7C.) under these con ditions
7. The anilinium sa3.t is the catalyst in the condensation reaction. It polarizes the carbonyl groups on SSE to form carbonium ions which can then react with OCA,
8. 2./27 -Cis'DAT in DT shows evidence of thermal degradation at 150-5C, This can be largely prevented by holding and transferring to pyrolysis at 120-5C.
DUP050081750
a
III. PATENT STATUS
The use of TFA Is covered by 157.2-K (allowed 10/18/67). A patent proposal is being prepared on the use of K-methyi~ aniline as a catalyst.
IV. SUGGESriOlS FOB FUTURE WORK
L Modify plant Jets to increase capacity so that a nitrogen sweep can be used.
2, Increase batch else beyond 216$ concentration,
V. DXSCUSS10H QF RESULTS
Results will be discussed in the order in which they occur in the synthesis,
A. SSB
No work was done on BSE. This is a well established process developed in the misubstituted quin&eridone studies,
B, Condensation
1, o-Chioranillne
The use of stoichiometric amounts of OCA and SSB resulted in a low yield of 2^.2'~ClsDiAT# Increasing the mole ratio of OCA;SSE to 4,5:1 gave yields In excess of 90$ of theory as ClaBQA, So further increases in yield were obtained by increasing the mole ratio beyond 5*5?X (see Table I), This data was obtained at 80-9OC./5O mm. Hg and using the o-chloranilirdm'a salt of TFA as catalyst.
TABLE X Effect of OCAsSBE Ratio in the Condensation on Yield
insafion teipera^.ure "SB^nJT"--~ Condensation pressure ** 50 mm Hg
OCA.; SSB
3.0:1 3*5:2 4.0: X 4,,5:1 5*0:1 5,5:1 6.0:1
Yield fas ClaDQA'
1 1 >in r n"ii,ii m.Tmi~iiiJfcn i i|ii ' i i ill i un .i'n
r<
?8.6$ 86.6$
89.0$
91.3$
91.2$
92*9$ 92,8$
DUP050081 751
* 3~
V, DXSCU3SIQrJ (Continued) B, Condensation (Continued'}
2 ,, Catalyst
Varying the concentration of TFA between the equivalence of 10 pounds/batch up to 40 pounds/ batch had only a slight effect on yield. This experiment was run at 80-90C./50 mm Eg, OGAsSBE of 5,$s'l and a 2-hour hold.
TABLE XI
A Concentration
Yield as
10# 90io
roo
s$ts
90$
30# $2$
40# 93$
The results in Table IX are estimated to be accurate to *1$ ,, Hence, the OCA-SSE condensation reaction does not appear to be rate controlled.
The amine associated with TB'A determines the effectiveness of the catalyst, TFA is a proton doners while the resulting enilinium ion polarises the carbonyl groups on SS38, The resulting earbonium Ion can then react with OCA to form ClsBAT, The use of a more basic amine such as N-methylaniline, as the catalyst, increased the rate of the reaction, but did not increase the optimum yield. Again, evidence that the reaction" is equilibrium controlled,
OCAiSgS 2,051 2.$0:1 5.50:1
TABLE III
Yield at C1SDQA WK^rr~^mmm
39$
65$
43$ 72$
95$
92$
DUP050081752
4
V. DISCUSSION fContinued)
B,, Condensation (Continued)
3 Time
During the first hour of the condensation at 80"S0C ,,/25 mm Hg# yield increased rapidly with time. (See Figure 1) Water removal now became limiting* since the concentration of water was within the solubility limits of the QCA~DT system. After 2 hours* there was no further increase in yields
4,, Pressure
Water removal is limiting in -the condensation reaction,, Its removal from solution depends on vapor pressure and rate of diffusion'. The vapor pressure can be reduced by reducing the total pressure on the system. This was demon**
strated by condensations run at 8o**90C At 50 rm of Eg* the yield as ClsBQA was 92% of theory while at 25 mm of Hg, it was increased to 95f> of theory. Since the yields could not be increased by running the reaction for a longer
period of time* this is a static effect.
The initial attempt to obtain a further increase in yield by decreasing the pressure to 10 mm Eg was unsuccessful. This was'found to result from a loss of the 0CATFA catalyst. By using the N-methyl&niiine salt of TFA* a less volatile catalyst* it was possible to run the reaction at 10 mm Eg, The following data further substantiates the effect of reduced condensation pressure on yield;
Pressure
Temperature
Y3 el A
50 mm Hg .10 mm Jig
95C, 95 C,
93 M 99.60
Based on these results* the reaction Is equilibrium controlled,
5 nitrogen Sweep
deducing pressure to increase yield is a static approach* since increasing the hold time beyond
DUP050081753
DUP050081754
5 **
V., DISCUSSIOH (Continued)
tKMHHsiwwiMkn^nunv*(>v< ^
V
3c. Condensation (Continued)
5. nitrogen Sweep (Continued)
two tours gave no further increase in yield. A dynamic method of reducing the vapor pressure of
water as well as increasing the diffusion rate is the use of a nitrogen sweep. Initial studies were run at a pressure of 25 mm Bg and 50 mm Hg respectively and a temperature of 80~90C. In both cases, yields were less than when no sweep was used. This again points out the volatility of the OCA salt of TFA.
The catalyst volatility problem was again mini-
missed by using the HHA salt in place of the OCA salt of TFA. Temperature and pressure were 80-*90G. at 50 Etna Eg, Nitrogen flows for two runs were 0.5 SCFH and 0.8 SCFH, respectively. These gave ClaEQA yields from SB'S of $6 Alfa and 9?. 3$, Under these same conditions, at 0,0 SCFH, the yield was
only 90,^$ Figure 2 is a plot of the increase in yield as ClaDCJA vs. the reciprocal of the SCF
of nitrogen put.through the system during the con densation . Extrapolation to se.ro water vapor pressure indicates that the maximum yield for the combined
condensation and pyrolysis is 99$ of theory. To . use either the static or the dynamic methods of reducing water vapor pressure to increase yield in the plant will require increasing the capacity of the vacuum jets,
6. Temperature
Yield, as C1BQA, increases with increasing con densation temperature up to a point. Above this temperature, yields decrease. The point of maximum yield is determined by the catalyst used. For OCA*TFA, this occurs between 80C, and 90 C! ., while for $HA.*TFA, it is very close to 95 *C. The greater volatility -of OCA *TFA was shown by the following TGA
results:
Catalyst .Salt Start to lose tyt. Wt4 Loss at 100C
CCA TFA
6oc.
30$
mm*Tm
8oC.
8$
DUP050081755
DUP050081756
/ V j TfZe>C,h/
DUP050081757
DISCUSSION (Continued) .
B,, Condensation (Continued)
6 ,, Temperature (Continued)
Hence, the maximum yield to be obtained by in creasing the condensation temperature is limited by catalyst volatility. Additional evidence for this is that yields decrease with decreasing total pressure above the critical temperature*
7,, Equilibrium Constant
The prior results indicate that the equilibrium is controlling yield. Since the equilibrium appeared to be unfavorable, a study was made to determine the equilibrium constant. The con densation is a two-step reactions
3SS + OCA ,pz> C1MAT + Hs0
CIMAT + OCA rn> Cis2A? + H20
The overall equilibrium constant Is then
he r~ he-hc_2
ClaDAT ^'Ha0
'j^V'dx<S^^un*?teKS(Sir<ivv<nuuAu.vCv.aK
SSE C0CA
The preliminary calculations were made from data obtained from running the reaction in refluxing SB alcohol* Similar rims were mads for DAT and. MesMT for comparison. Since the results were based on product yield,, the equilibrium constants were considered to be approximate values for the
overall condensation reaction
Product
kc
2,2*-ClgMT
0,06
DAT 11
MegB&T
78
An .assumption was made in calculating these values that only 10$ of the product was in solution. These
results indicate that .all three condensations are probably equilibrium controlled and the 2s29~fllgMf equilibrium is particularly unfavorable,,
DUP050081758
I*>v
1 0. ,
fiJl-t-r(ti-P
| ( S S S (t*/> r/tn u )
[' (*)
1.(3). 32 -/ Hey
{in) Sr 6. 0%"/* tiC/
` (S-J) Coi* ^ Hef/cc
j (Q Uzd
* (h )-C*X2.).4 IS'-
I ( 7)
Xm
f\A-tlv*stSsSt&cJ
'* M-tO
\(}o) H"l C> Cu^t~dlsPl'V/*v^ ) S ,,&($) -h (0)
160 s*e(
) * CO-(h )
6^ CUUi *
)s. (*)-a(9)
jj fl3) H*A^rpC^ti' A-- /$4~Ctssitis C?t l (l ) ^
Oh ) X* 0*X**)Yt>ix^)
b. $U-> Qrvti&s
Cfx P&7
OW T
n <3.^0 a 7
) t (Z (r O /\n>*ir&Q /1 #2< O /Irydtn
2, ?.7 15^J>
/, /**,sr
3.1gi " 3.1$o ~ 32,S'^JI 3 2, t, srti? It / sits' a tzsr
< V*0 / 0, &/ /0^Jcc 0. ys~/6 g-Ac
0 I 0/V IH i ,2.<j. VO"
j, 73^/w ^j | // 3 3<? /Tr-tizs SIS,2^
3*/6> |
3 %t sp\t-@ur ), J. 0 ltw&t\ 1 > 2 V
t
h 3 * 1&Hct>^tit<)\ 3, $ 'J'R r,n/~di
0,11)
0,012> sr*tita 0,o.M/*&*..
2,30s) snvti# ]1 tf,0 1 (Tmtiis* 1,2 S3
0, 032/jtVLrtiL, 0
0,O<*
11
Q * 1Z^fC* /tri't'U*? i I 72
^5<r
OCH
or
CIL OAT (AOJ)
CU 0#T(*>dr>,)*
jc/Mir
(,enti~4^,/ti^)
f*l 0 { ?vvtf^ *
^
A S2(* sr**Oo 11 2*)y sr,\rk<3 0 , Q 40 s),\ <'&o 0, 00 O ftvvdti 0 i OQQ Q * QO p /yv\/p&*0 0 * 0 P & sy**
jirtvJ'Ch^ ^ ct.ofay .tPCow~*S
01 2^i " dj ZS'it'*0,'61-fz 0. Oo^ryt^r/t-, l, 570 - 0-S27 * A f 3^ ^
1.2ct~? swtilt. T" ty&S * 0 *2S( fynr&s. , * O # / / O' <0.t S3?'-&(*>*&) r O, A $^0L
0)531 yr^A 0* &$^r ^
H, ejt 08"c .
DUP050081759
DUP050081760
C.CS7
6'C ti,
6 ,U &
WW
i> -0 ^ 0.3$S
Co /y-v^-Q-"Ci! .C~ic) '"'
JO T ~h & */~}
. . . i. .
yyvs><>-<ss^<- Cv'^')
2
--- C 83
~ Z 3 3 Cs
ffor
JfPOG.19
1.^7/ \ Z. 33 6- C/* v - >,
//Q3? 2,33 <3
(f/4 #>) *
Si?, sr~
//c
+ jpp^ = 5?`"'<:5 ~0*C *-
S
^ Jp*^ ss' >
} *), 2, HB7 ~ 0*03
/v /r ^4-
(ohr) s o,
tyV\&,pj4orrv*r-- ^2*P. <--< |
j
/Vtf^ts$sr>-* - (^, 'X& < 2*3 (a^j * 65 , 3" ?^ -r^rbf
yr /w w k 4u 4 fafcdP
<C 6, &7 2,
/VyVtf^ytvnrV'.~......
C--
* 6?/ t "? 2, * 0, <S 3*7
^
/,
, _^3>
?*<* /n-rT
P'ftnv.o *
y .
P~ **P
s 7.o
Yptty
rt.2-7.0 * A2.2,,
, <5 3 5*" svu*~&* ^i*
i/y/
^
/C^j u
DUP050081761
j&(L. ^C*^t'\supt-"f'^t--,,_. 0SJ i #'&% **--,
^^t^^j?v>va<v---->
; ^ (o. )n>)(o,o*sr-)'i-` ^c (o^oO'SjCh * 3<>yc 51 & * oz-sr
DUP050081762
DISCUSSION (Continued)
B. Condensation {Continued)
7. Equilibrium Constant (Continued)
To improve the accuracy of the ClaBAT equilibrium constant, the reaction was run in Bowtherm where the solubility of ClaBAT and yields of ClsDAT and HaO could be determined. Based on thsse results, the equilibrium constant was equal to or less than 0.025.
C . Pyrolysis
Normal laboratory pyrolysis conditions (M-67-11) using a ClgBAT/BT transfer temperature of X50~5oC. gave good
yield (95*9$) and quality. Quality is based on the appearance of the ClgDQA and the clarity of the MeQH-BT
filtrate. Under laboratory conditions, the ClaBAT is held at elevated temperatures for short periods of time in comparison to the plant. To check out the stability of ClaBAT in IT, it was held at 150-5C for 24 hours prior to pyrolysis. In comparison to the normal minimum hold, the yield decreased 4.6$ to 91*3$ and the amount of WU found in the pyrolysis equipment increased. Hence, at 150-5C., ClaBAT degradation takes place. This can be minimized by lowering the ClaBAT transfer temperature,,
In a similar experiment in which the CI2BAT/ET was both held for 24 hours and transferred at 120-5 the yield of ClgBQA from SSE was 9^.4$. Hence, at the lower temperature, little or no degradation takes
place.
REFERENCES
Additional data may be found in the following references
1 Condensation
a. OC&iSSE Ratio
4.0:1 to 6.0:1 42 3.0:1 to 4.5:1
b. Catalyst
5125-39 -40 -41
'52
TFA concentration St tJ
Synthesis TPA*OCA salt n TFA'NMA salt
MA .TFA Effect of amine basicity
DUP050081763
VI. EBFEESKCES (Continued)
I. Condensation (Continued)
c Time
5125-48 "56
30 30
(80-90o C,/25 nun Hg)
d. Pressure
5125-55 *66
"72 "81 -88
10
25 10 50 10
e Nitrogen Sweep
512-5-60
"6l
-68
-71
P ~ 50 mm Hg (TEAOCA catalyst P * 25 mm Hg (TFA-OCA catalyst
0.5 SCFM/50 mm Hg/TFA* 0.8 SCFM/50 mm Hg/TFA
f. Temperature
5125-43 "44 *.45 46
-81
-85 "88
85-l40C. 70-95C./50 mm Hg 100"10 C o/50 mm Hg ?0"90*C ,/25 mm Hg
100-20cC./50 mm Hg/M 95-H5'C./50 mm Hg/TFA-MA 92-i2bC,/50 mm Hg/EFA*BMA 92-115 C./10 mm Hg/TFA*3SMA
g. Equilibrium Constant
5125-58 59
-62 "65
67 ...69
4,4*-HeDAT DAT
2r2'-C.laM0? CIeSAT solubility in 0CA/OT CljsDAT solubility in 0CA/2B aleobol Effect of temperature on equilibrium.
2,
5X25~|3 70
Effect of 0,05$ OCA endpoint Increase distillate for better OCA
removal Composition of 0CA/DT distillation
DUP050081764
9
vi* BEFJ2RSMCSS (Continued)
3,, Pyrolysis yhlnuwii***
5125-51 100
Pyrolysis of isolated ClaDftT Transfer temperature
k, DPI)' Formation
5-125-^9 ~5v
-73 -S3
Slow addition of excess OCA ClsDAT -5* OCA at elevated temperatures
Hold at temperature prior to adding TFA Virgin Dowtherm
Miscellaneous
5125-^7 -50 -75
ClaDQA fluorescence 2,25 ~C1SDAT synthesis and isolation 2,2'-ClsDAT standard Attempted removal of water by benzene azotrcph
DUP050081765