Some Sulfonamide Plasticizers and Waxes DAVID AELONY Chemical Laboratories, General Mills, Inc., Minneapolis, Minn.
A
LTHOUGH readily available and relatively inexpensive, aromatic sulfonamide derivatives have received but scant attention from the manufacturers of plasticizers and waxes. Van Antwerpen ( 5 ) , in his summary of commercially available plasticizers, lists but two aromatic sulfonamide derivatives, Santicizers 8 and 9 (mixtures of 0- and p-toluene-N-ethylsulfonamide, and mixtures of 0- and p-toluenesulfonamide, respectively). Reed, in an excellent paper (4), lists but one sulfonamide derivative, S-n-butylbenzenesulfonamide (Santicizer 127), and Bergen and Craver ( 1 ) discussed mainly the lower -V-substituted alkyl sulfonamides and the sulfonamide aldehyde resins. There is no record of a concerted effort to correlate the structure of aromatic sulfonamides and their performance as plasticizers and waxes. To rectify the situation several series of compounds were synthesized and tested for plasticizing action on vinyl resins and for waxlike properties. The compounds prepared may be represented by the following formulas. RSOzK( C2H.iOCOR')Z
(1)
where R is phenyl, tolyl. 4-chlorophenyl, 2,5-dichlorophenyl, 2-naphthyl, cr thienyl; and R' is heptadecyl, methyl, propyl, or propenyl.
R" CnHIOCOR' where IZ is phenyl or tolyl; R' is heptadecyl, tridecyl, undecyl, nonyl, heptyl, propyl, or methyl; and R" is hydrogen, alkyl, or phenyl. RSOnNR'R"
(3)
where R is phenyl, tolyl, sec-octylphenyl, 2-naphthyl, amylnaphthyl, 2,5-dichlorophenyl, tetrahvdronaphthyl, or thienyl; and R' and R" are H, alkyl, or alkenyf. R ( S0JiR'R")n (4) where R is phenylene and R' and R" are either hydrogen or alkyl. Because a large number of compounds were prepared, only one member of each series is described in det,ail. Tables I and 11, however, give yields and properties of all the compounds prepared and tested. PREPARATIONS
LvjA!7DI -,8- HYDROXYETHYL-P-TOLUENESULFONAhlIDE DIBUTYRATE. S,S-Di-p-hg~droxyethyl-p-toluenesulfonamide ( 3 ) ( 100 grams], n-butyric acid (70 grams), xylene (250 ml.), and ptoluenesulfonic acid hydrate (0.5 gram) were agitated and refluxed over a Stark and Dean tube for 4.5 hours. Fourteen milliliters of Tvater was collected in the trap (theoretical). Xylene was evaporated and the residue was distilled in vacuo. The distillate weighed 118 grams (76.6% theory); boiling point a t 0.4 mm., 238" C.; ng 1.5002; per cent nitrogen found, 3.52 (theory 3.51). N-ETHYLS -P-HYDROXYETHYLBEA-ZENESCLFOXAMIDE MYRISTATE. Benzene sulfonyl chloride (353 grams) was added drop by drop (during 145 minutes) t o a boiling, agitated solution of 225 grams of soda ash and 178 grams of ?i-ethyl-N-p-hydroxy-
ethylamine in 1.0 liter of water. The mixture was refluxed and agitated for 2 hours. It was extracted with benzene, washed with water, dried over sodium sulfate, filtered, and evaporated. The residue was distilled a t a pressure of 0.1 mm. of mercury. It boiled a t 169"; ng 1.5378; hydroxyl number 245.8 (theory 245); amine number 0.28; per cent nitrogen found 6.05 (theory 6.11). The distillate weighed 402 grams (87.8% theory). The residue weighed 15 grams; ng 1.5493. The distillate was 2V-ethy1-,17-
p-hydroxyethylbenzenesulfonamide.
The distillate (114.5 grams) was refluxed for 2.5 hours with 113 grams of technical myristic acid, 5 grams of p-toluenesulfonic acid hydrate, and 300 ml. of xylene. The product was viashed with water, aqueous alcoholic ammonia, and water. It was dried over sodium sulfate, filtered, and evaporated. The residue was distilled a t 40 to 50 microns. Fraction 1, boiling point a t 40 mm., 225' C., weighed 17 grams. Fraction 2, boiling point a t 50 microns, 240' C., weighed 192 grams n z 1.4915. Saponification equivalent 443 (theory 439); per cent nitrogen 3.14 (theory 3.18). The yield was 87.9%. ,V - ETHYL - s - - HYDROXYETHYLBEA-ZENESULFON.4llIDE CAPRATE. One mole of benzenesulfonyl chloride was dissolved in 200 ml. of benzene and was slowly added to a solution of 234 in 400 ml. of benzene. grams of X-butyl-~l~-~-hydroxyethylamine It was refluxed 3 hours, washed with 45 grams of sodium hydroaide, dissolved in 300 ml. of water, washed with mater, dried over sodium sulfate, filtered, evaporated, and distilled in vacuo, yielding 237 grams of distillate (92.2%). Boiling point a t 40 to 70 microns, 169-78" C., 1.5247; per cent nitrogen 5.45 (theory 5.45); hydroxyl number 217.6 (theory 218.3). N-Butyl-S-@-hydroxyethylbenzenesulfonamide thus prepared (129 grams) was refluxed for 3 hours over a Stark and Dean tube with 86 grams of technical capric acid, 5 grams of p-toluenesulionic acid hydrate, and 300 ml. of xylene. The product was washed with water, dried over sodium sulfate, filtered, and distilled. The distillate boiled a t 209-11' a t 30 microns, n z 1.4927. The yield of the distillate was 193 grams (94.4%); saponification equivalent was 412.8 (theory 411). S-PHENYL-N-~?-HYDROXYETHYLBENZESESULFOXAMIDE ACETATE. Benzenesulfonyl chloride (188 grams) was dissolved in 300 ml. of benzene and added a t once to 147 grams of distilled N-phenylethanolamine. The temperature rose to 45". Then 100 ml. of pyridine was added and the temperature rose to 85". The product was refluxed for 3 hours, cooled, washed with 90 grams of sodium hydroxide dissolved in 400 ml. of water, dried over sodium sulfate, filtered, and evaporated. The residue was a viscous yellow liquid weighing 277 grams (93.6%), ng 1.5838: per cent nitrogen found, 5.02 (theory 5.08); amine number 0.19. Seventy grams of this residue was refluxed 5 hours with 80 ml. of acetic anhydride. After distilling off a mixture of acetic acid and acetic anhydride, 75 grams (93% theory), ng 1.5570, distilled a t 185-8' at 30 microns. Per cent nitrogen found, 4.31 (theory 4.39). X-OCTADECYLBENZEA-ESULFONAMIDE. Technical X-octadecylamine (134.5 grams) was dissolved in 300 ml. of benzene and agitated with a solution of 22 grams of sodium hydroxide in 100 ml. of water, while 88 grams of benzenesulfonyl chloride was added a t a rate causing slow ebullition. Agitation and reflux
INDUSTRIAL AND ENGINEERING CHEMISTRY
588
Vol. 46, No. 3
TABLE I. CONPOCKDS PREPARED R
Yield, %
Ri
4
B.P.
% N Found
7c K
Sap. Eq.
Celcd.
Found
Sap. Eq Calcd.
CzHaOCOK'
Series I.
/
.\~,N-Di-8-hydroxyethyl Aryl Sulfonamide Diesters, RSOzN
\C2HIOCOR'
0
CHI
88
CzHi
966
CsHs
....
176.5
1.S10330
4.02
3 97
238405 p
1.500230
3.52
3 j1
82
2354,o p
1 523280
3 68
3 54
206.4
197.5
CHs
75.2
192-20350-70
1 .,51833o
4.24
4.18
176.9
167.5
CHr
72.0
227-3213
1.30:3525
..
..
278.4
283
277.5 312
271 299
383 41 1 439
p
177.7
_..
6'
C
l
O
p
Series 11. S-Ethyl-.~-5-liydlos).ethylbenzenesulfonamide Esters, S02N
/C2H6
'CnH;OCOR 95.5 83 54 7 b 84 27 3 C 87 8 94d 72.7e
CHs C3Hr CrHin CsHis C12H15 C14Hns CisHai CieHas
1 8 4 p~ 1 soin0 iL
177-8210
p
225230 p
215-20,o 24060p
?42;c
5.09 4.68 3.95 3.67
5.16 4.68 3.94 3,65
3:i4 2.79 2.80
3:is
3i3:3 41 6 443
2.81 2.84
488
493
4.68 4.28 3,65 3.41
181.8 329 6 395 412.8
187.6 327 383 41 1
5.16
277.5 181.8
271 187.6
p
$
....
...
...
...
CiHs Spiies 111. S-B?ityl-~-8-hj-dl.os~-ethylbenzenesulfonamide Esters,
78.5 83.5 ,
. .P
93.9
Series IT.
153-4s p 155-701p-in 184-9210 p 200-113~p
u ,
1,507530 1,502525 1 ,494525
...
4.68 4.26 3.71 3.37
>\'-Alkyl (or Aryl), N-5-Hydroxyethylbenzeneeulionamide Acetate,
1.513380
95.5
1 ,507530 1 557025
78.5 93.0
5.09 4.58 4.31
4 68 4,39
...
Series 1'. A'-Alkyl Aryl Sulfonamides Same S - B u t y l benzenesulfonamide ,\r-Dodecyl bensenesrlfonamide ,V-Octadrcyl benzenesulfonamide Ar-Octndeoy1toluenesulfonamide .?--OetyI naphthalenesulfonamide
1I.P. 1.521330
86.4
...
84 93
... ...
86 89.3 Series VI.
Diallylben7enesulfonamide Dihutyl benzenesulfonamide Dicyclohexyl benzenesulfonamide Didodecyl beneeneeulfonsmide
6.48 4 06 3.36 3 26 4.34
6.57 4 30 3 42
3 31 4.34
...
54,5-7 81 g3-4 ,3-4
N,N-Dialkylbenzenesulfonaniides 5.90
5,20
94:G 26 t 53.6
4.36
.. 1G6L2
S, S-Dialkyl Alkj-l Benzenesulfonamicles
Series T'II.
d 91 i h"~-Dihutsl-p-toluenes~lfonamide 91.7 92i d e ~~~'~~-Diootyl-~-toluenesulfo~am 40 N:N-Dibutyl-Tetralin sulfonamide 86 A-,N-Dioctyl-Tetralin sulfonamide A', N-Diethyloctylbenzenes~il68 fonamide A', A--Diethyldodecylbenzene36k sulfonamide N. Y-Diethyl-p-toluenesulfonamide V-Diethvl-n-toluenesulfonamide S
1193s p
4: 94 3.54
1.048 0.9788
14050 tl 222-426
$A
1.491330
3.47
178-8031 p
1 .5313*6
230-5rc
p
1.511025
3.97 3.16
4.33 3.22
4.25
4.30
1.0189
3.43
3.67
0,9895
5.05 3.62
1.11Q2: 1.G19S2: 1.220
1 .jhj330
160-325 ,u
20pa3
1 ,504025
1,497380
4:kG
1.1149
1,0051
Serien 1'111, hIiecellaneous N,S-Dialkyl Aryl Sulfonamides N,N-Dibutylthiophenesnlfonamide N,A--Dioctylthiophenesulf onamide S,,\'-Dibutyl-2,5-dichlorobensenesulfonamide N-n=Dibutyl-2-naphthalenesulfonamide1 ~-All~l-N-octyl-2-naphthalenesrilfonamide
92 71
14750 p 200-576
I ,511026 1 .4'i4025
p
4.93 3.58
85
17060 i.i
1.628R8o
3.97
4.20
81.5
20oioo tl
...
4.34
4.34
91
208-1040
3.96
3.90
fi
1 .5:7s25
... 1.0811 (Contznued on p a g e 589)
INDUSTRIAL AND ENGINEERING CHEMISTRY
March 1954
589
TABLE I. (Continued) Yield, %
Name
,V, N'-Dibutylbenzenedisulfonamidem N,N,N'.A;'-Tetrabutylbeneene
7i N Calcd.
d
8.04 6.0$
...
Di- and Tetraalkyl Benzene Disulfonrtmides
85
7.91 5.88
1.;O3830
225-30,;',
91
3' % N Found
n&
B.P. Series I X .
Series X.
...
"axe? 1I.P.
N-@-Hydroxyethylbenzenesulfonamide stearate A--@-Hydroxyethyl-p-toluenesulfonamide stearate ,\',1V-D~-B-hsdroxyethylbenze~~esulfonamide distearate A', ~r-Di-8-hydroxyethyl-4chlorobenzenesulfonamide distearaten A' "f-Di-@-hydroxyethyl-2,5-dichlorobenzenesulfonamide distearate ~.1V-Di-8-hydroxyethyl-p-toliieneiiiifonamide distearate _.~~..~ A', N-Di-8-hydroxyethylthiophene sulfonamide distearateo N , A~-Di-8-hydroxyethyl-Znaghthalenesulfonamide distearate ~~
Acid KO.
71
2 97
3 02
79-79.5
99
2.89
2 97
Buttery consistency
98
1.74
I 81
75-6
100
1.74
1.74
84.5-5
91
1.66
1 67
72-5
5.7
92
1.76
1.78
68-9 5
2 4
1.76
1.80
73 5-77
6 0
1.68
1.70
78.5-80
1.34
... 78
f Mechanical loss. Q Contaminated with a little monoallyl compound. h d;' 1.0638. N o attempt was made t: obtain a good yield. 'Y Melting point 57.5-62.5
dO : 1.1966. b Mechanical loss accounts for low yield. c Prepared from acid chloride and pyridine, acid No. 3.4. d Butterlike solid, acid N q 3.0. e Could not be distilled without decomposition.
a
.
4.7
13 6 1 2
k Over-all vield from dodecyl benzene 1 m n
Melting-point 51-51.j0. Melting point 98-101O. O H KO,10. O H 3.43 mechanical loss.
TABLE 11. EVALUATION O F PLASTICIZERS %
R
R Series 1.
..
C1
Series I1 Ester Radical Acetate Butyrate Caprylate Caprate Lanrate Myristate Stearate
\
CsH4OCOR'
....
....
Hard
Fairly hard
N O
NO
.. No No
NO N O
No No
h-0
Very slight
NO
Oleate Series 111 Acetate Butyrate Caprylate Caprate
75 70
++ 51
48'
+'z
..
*.
100 124 115 105 104 83 68
73
Series V I 1
IV
- 6 - 9 -12
-16 -19
- 20 - 6
-18
.V-Butyl-N-hydroxyethylbenzenesuifonamide Esters No 114 - 7 N O 109 - 9 KO 111 - 14 ?*TO 95 -13
A;-Alkyl
(or
JV .V-Dialkyl Alkyl Benzenesuifonamides
N ,N - Diethyl- p-toluene suifonamide N,N-Dibutyl-p-toluene sulfonamide N,N-Dioctyl-p-toluene sulfonamide N,N-Dibutyl Teu-alin sulfonamide A;. A'-Dioctvl Tetralin sulfonamide N,N-Diethyloctylbenzene sulfonamide N,N-Diethyldodecylbcnzenesulfonamide
Series VIII. Series
N..V-D alkylbenzenesulfonamides
Name
N-Ethy1-,Y-hydroxyethylbenzenesulfonamideEsters
N O
Aryl) N-@-hydroxyethylbenzenesiilfonamide Acetate NO N O
KO
Series V Same ,V-Eth ,l-p toluene sulfonami& (Santicizer 8) N- Dod eoyibenzenesulfonamide N-Octadecylbenaenesulfonamide N-Octadeoyltoluenesulfonamide
100 3 114 30.2
-- 76 +I3
"?-Alkyl A r y l Sulfonamidep
Hard knd brittle Hard and brittle
Sweats
..
..
69
+3
60
-16
I
.
..
N,N-Dibutyl-2,5-dichlorobenzenesulfonamide N,X-Dibutyl-2-naphthalenesulfonamide AT-Allyl, N-octylnaphthalenesulfonamide
Series IX.
...
NO
90
+7
, . . .
N O
135
- 3
...
NO
95
Incompatible
.. ....
..
..
- 17 ..
So
59
- 3
NO
85
- 5
NO
61
- 1
Miscellaneous N,!V-DialkyI Aryl Sulfonamides
N,.V-Dioctylthiophenesulfonamide
R N-Ethyl Ar-Butyl N-Phenyl
Sweating in 24 Hours
Diallyl Dibutyl Dicyclohexyl Didodecyl
/
RC&-SOzK
CHI CaH7 CsHj CHI CHa
CHa CHs CH
Series VI.
"v7.N-Di-6'-hydroxyethyl Aryl Sulfonamide Diesters C~HIOCOR' '
Remarks
Elongation a t 1000 MiniLh./Sq. mum Inch Flex, O C.
.... Incompatible
79
K O
..
-21
..
....
NO
47
$12
....
NO
60
+2
Di- and Tetraalkyi Benzenedisulfonamides
N,N'-Dibatylbenzenedisulfonamide N,N,N',N'-Tetrabutylbenzenedisulfonamide
Incompatible Comp. b u t hard
,
..
..
..
..
..
,
590
INDUSTRIAL AND ENGINEERING CHEMISTRY
were continued for 5 hours. The product mas poured into a separatory funnel and the aqueous layer was drawn off. The benzene solution was washed with water until it was neutral, dried over sodium sulfate, filtered, precipitated with alcohol, cooled to 15', and filtered. The mother liquor was evaporated t o 500 ml., cooled to 15", and filtered. The second mother liquor was discarded. The first crop of cryst,als weighed 126 grams, melting at 81'; per cent nitrogen, 3.36 (theory 3.42). The second crop rreighed 48 grams, melting a t 76". The second crop was recrystallized from 300 ml. of alcohol. It weighed 35 grams, melting a t 76-7'. i\;o attempts were made to identify the second crop further. On the basis of the first crop alone, t#hc yield was 67.3% of theory. I \ ' , N - D I B V T Y L B E ~ Z E ~ E S U L F OBenzenesulfonyl S~~~IDE. chloride, 176.5 grams dissolved in 200 ml. of benzene, was slowly added to a mixture of 50 grams of sodium hydroxide dissolved in 100 ml. of mater and 129 grams of dibutylamine dissolved in 100 ml. et' benzene. The reaction \vas very exothermic. The product TT-as allowed t o stand 1 hour with occasional shaking. It was washed with water, dried over sodium sulfat,e, filtered, evaporated, and distilled through a 12-inch Vigreux column. After a 5-gram forerun, smelling strongly of dibutylamine, 243 grams (90.3% of theory) distilled a t 125-55' at 35 t o 70 microns; n g 1.5016: dtO 1.0638; per cent nitrogen 5.07 (theory 5.20). The residue weighed 6 grams; ng 1.5046. N , N - D I - n - O C T Y L - T ~ T R . i L I ~ SVLFO IIDE. Tetralin sulfonyl chloride (100 grams), 105 grams of di-n-octyl amine, 40 ml. of pyridine, and 250 ml. of benzene were refluxed 20 hours. The product was shaken with a sodium hydroxide solution. It was washed, dried over sodium sulfate, filtered, and evaporated. It distilled a t boiling point at 30 microns, 230-5', weighing 147 grams (86% theory). n g 1.5110; per cent, nitrogen 3.16 (throry 3.22); dZo 1.0051. N , S - DI - n - O C T Y L T H I O P I I E S E S ~ ~ L F O S ~ ~ f I DThiopheneE. sulfonyl chloride (77.5 grams) was dissolved in 100 ml. of benzene and was added with stirring t o a solution of 205 grams of di-noctylamine in 400 ml. of benzene. The temperature rose to 80", and the salt began to separat,e immediately. The mixture was allowed to stand overnight. It was washed with alkali. washed with water, dried over sodium sulfat,e, filtered, evaporated, and fractionated in vacuo. One hundred and seven grams of di-n-octyl amine was recovered. The distillate weighed 116 grams (71% theory). Boiling point a t 75 microns, 200-5'; n?; 1.4940; d;: 1.0198; per cent nitrogen 3.57 (theory 3.621. There was an intermediate fraction weighing 11 grams and the residue weighed 12 grams. , 1 - , N ! N ' , N ' - T E T R A - n - B C T Y L B E S Z E I ; E S U L F O ~ ~ ~ ~ l I D EDi-n-butyl. amine (225 grams) was added slowly with stirring to a solution of 117 grams of benzene disulfonyl chloride in 1.0 liter of benzene. The reaction LyaS exothermic. The product was allowed to st'and 1 hour, then washed with water, dilute acetic acid, dilute sodium carbonate, and water, dried over sodium sulfate, filt'ered, and evaporated. The residue !vas distilled in vacuo, yielding 1'78 grams (91% of theory). Boiling point at 10 microns, 225-30"; n g 1.5038; per cent nitrogen 5.88 (theory 6.08). The distillate was treated v-ith Norite and filtered. The filt,rate was ~vatcr white. N,?vr-DI-8- HYDROXYETHYL- p-TOLUENESELFONb3IIDE DISTEARATE. S,S-Di-p-hydrosyethj-1-p-tolueneeulfonaInide (518grams 1, commercial 90% stearic acid (10% grams), p-toluenesulfonic acid hydrate (10 grams), and 1000 mi. of xylene were agitated and refluxed over a Stark and Dean tube. Theoretical amount of ivat,er was collected in 3 hours. The product \vas diluted to '7.0 liters Tvith xylene, brought to a boil, and filtered. Ten grams of xylene-insoluble material was thus removed. T h e filtrate was alloived to cool and was filtered. This first crop was recrystallized once more and yielded 543 grams of a transparent straw-colored wax melting a t 69.5": acid number 0.26; per cent nitrogen found 1.74 (theory 1.78). Second crop was a brown wax. It weighed
Vol. 46, No. 3
227 grams melting a t 68.5-69.5"; acid number 1.2. Third crop weighed 186 grams melting a t 66-7.5"; acid number 2.6. The third mother liquor jTas evaporated to drj-ness, yielding 522 grams of brown translucent wax, melting at 61.5-65"; acid number 7.4. The total yield was 97.6% theory. Table I summarizes yields, boiling points, refractive indice., densities, melting points, and analytical data of all the compounds prepared. The yields given do not represent maximum yieldi, because most of the preparations were run but once. Attempts were made to prepare reasonably pure materials. The higher fatty acids used in esterifications m r e generally 90% pure. The octyljenzene and t,he dodecylbenzene derivatives were prcpared from Eastman's caprylene and 1-dodecene, respectively, b ~ Friedel and Craft's reactim. The amines w e d n-ere comniercially available and n-ere not further purified. EVALUATIOS O F PLASTICIZERS
All of the plasticizers Ivere evaluated as follows: Thirt,y-five grams of plasticizer ovas mixed and milled on a heated roller mill at 140" t,o 50" with 63.5 grams of Vinylitc V P S W (Carbide and Carbon Chemicals Co.), 0.5 gram of stearic. acid, and 1 g a m of basic lead carbonate. Twenty-four hours after milling, the sample3 were examined for "sweating" by tho cigarette paper method of Reed ( 4 ) . Plasticizing efficiency was estimated by per cent elongation at 1000 pounds per square inch, tested on a 0.025 X 0.080 inch sample in a Scott paper testing machine a t 72" F. (load applied in 55 seconds). Minimum fieu temperature was measured according to Clash and Berg ( 2 ~ ) . Heat &ability varied so much viithin series that lack of it in some cases is considered to be due t o small amounts of impurities. It is, therefore, not reported here. DISCUSSION
PL.ASTICIZERS. T h e emphasis in this investigation was put on the relationship of chemical structure with compatibility, elongation, and minimum flex temperahre. Heat Btability \vas measure3 and found to be satisfactory (at least 1hours a t 160" C.) for most of the compounds tested. I n several instances, however, it x a s surprisingly poor (15 to 30 minut,es a t 160' C,)> considering that neighboring members of the same series had ver3satisfactory heat stabilities. Poor heat stabilities xere, therefore, ascribel to the presence of impurities which caused discoloration. S o attempt x-as made to study the volatility of plasticizers ized repins, nor to study the extractability of the plasticizers by water or solventP. It was felt that while some of the products described possess reasonably good propert,ies as plasticizers, t,he important thing is to establish broader generalizations as to the relationship betiveen the structure of the plasticizer and compatibility, elongation, and minimum flex temperature. The conclusions reached apply only to the resin tested, Vite V Y N K . Bergen and Craver ( 1 ) mentioned that the cIi-substituted aryl sulfonamides are generally less compatible vvith various resins than the .V-mono substituted aromatic sulfonamides. T h e tables presented here do not indicate that thr mono alkyl aryl sulfonamides are better plasticizers for S'inylite VYSTV; on the contrary, loner minimum fle crature and higher per cent elongation are noted for eom dialkyl aryl suIfonamides. The author's experience 133th 'cyclohexylbenzenesulfonamide coincides, however, with the opinion cxpressed by Bergen and Craver that .V-substituted cyclic groups of aryl sulfonamides tend to give compounds of high melt'ing point which results in poor compatibility. X a n y of the series presented are too short for valid conclusions, but they were included to indicate general trends. An examination of Series I to IX, inclusive, shows that ahile one sulfonamide grouping per molecule enhances the plasticizing properties, t x o sulfonamide groupings per molecule are hardly
March 1954
INDUSTRIAL AND ENGINEERING CHEMISTRY
advantageous. The same applies to a lesser degree to ester groupings, one ester grouping per molecule being more desirable than two. These deductions apply, however, to compounds of a certain molecular weight range. If this range is greatly exceeded, the above statements may no longer be true. The N-ethyl-AT8-hydroxyethylbenzenesulfonamide esters show up somewhat better than the corresponding N-butyl derivatives of the same molecular weight. It would be of interest to compare them with iY-methyl and AT-propyl derivatives. The oleate ester in Series I1 is somewhat better than the stearate in per cent elongation and is far superior to it in minimum flex. It euggests that the dodecenate may be far superior to the laurate. The homologous series of Series I1 and Series I11 shows that unfortunately maximum values for elongation do not correspond to minimum values in minimum flex temperature and that a compromise choice may have to be made. It is evident that when phenyl is substituted for an alkyl in .V-alkyl-Ar-(3-hydroxyethylbenzenesulfonamideacetate, much poorer elongation and much poorer minimum flex result (Series IV). Comparing compounds of approximately the same molecular weight in Series VII, i t is evident that N,Ar-di-n-octyl-p-tduenesulfonamide is a much better plasticizer than ilT,N-diethyldodecylbenzenesulfonamidp. N,N-Dialkyl Tetralin or naphthalenesulfonamides make poor plasticizers (Series VI1 and VIII). Thiophene derivatives Ehow promise, but not enough individual compounds have been tested to show that they have a real advantage over the cheaper benzene derivatives. Kuclear chlorination makes a t least the lower molecular weight members of N,.V-dialkyl aryl sulfonamides incompatible with the Vinylite resins. N,Y-Dialkenyl compounds are apparently no more desirable than the N,N-dialkyl compounds (Series VI). The limit of compatibility of X,N-dialkyl aryl sulfonamides and the Vinylite resins is reached somewhere between h',"Vdi-n-octyl-ptoluenesulfonamide and K,N-didodecylbenzenesulfonamide, Series VI and VII. W ~ X E S .J17axes are valued primarily for their physical properties. Their chemical conqtitution i p of little interest to their
591
users. Their main users are manufacturers of paper products, polishes, electrical equipment, carbon paper, and textiles. The properties desired thus vary with the use to which a wax is put. The usefulness of the waxlike materials prepared was examined only a i t h respect to polishes. Waxes are used in polishes chiefly as wax-in-water emulsions or as gels of wax in solvents such as turpentine, and mineral spirits. A11 the waxes listed, a i t h the exception of the thiophene one, gave reasonably good gels with turpentine or mineral spirits. All imparted good luster to leather, nood, and metal surfaces. \Tax gels made from Ar,K-di-p-hydroxyethylbenzenesulfonamide distearate synergized on standing a t high room temperature (30" to 50). When a gel was made from X-dodecylbenzenesulfonamide it did not produce any shine on leather, wood, or metal surfaces and destroyed shine imparted to those surfaces by waxes. However, N-octadecyl-p-toluenesulfonamide imparted good luster to wood but a poor luster to leather. The gels were generally prepared by pouring 25% solutions of the wax in turpentine or in mineral spirits at 40' to 50". Emulsions in which anionic agents, such as morpholine oleate, were used had a tendency to thicken to gel on standing. Considerable dilution a i t h LTater would not materially thin the gel. It is thought that the thickening is due to the reversion of the oiI in water to a water-in-oil system. ACKNOWLEDGMENT
The author wishes to thank D. H. Vheeler for encouragement and cooperation. Analytical data and evaluation were done under the direction of Harold Boyd. LITERATURE CITED
(1) Bergen, H.
(2) (3)
(4) (5)
S.,and Craver, J. K., IKD.ENG.CHEM.,39, 1082-7 (1947). Clash, R. F., and Berg, R. bl., Ibid., 34, 1218 (1942). Pearock, D. H., and Dutta, U. C., J . Chem. SOC.,1934,1303-5. Reed, M. C., IND.EKG,CHEM.,35, 896 (1943). Van -4ntwerpen, F. J., Ibid., 34, 68-73 (1042).
ACCEPTED December 2, 1953. RECEIVED for review August 5 , 1953. Paper 156, Journal seriea, Research Laboratories, General Milla. Inc.
Displacement of Petroleum from Sand Surfaces by Solutions of Polyoxyethylated Detergents H. K. DUNNING, H. J. GUSTAFSON, AND R. T. JOHANSEN Surface Chemistry Laboratory, Petroleum Experiment Station, Bureau of Mines, Bartlesville, Okla.
I
N R E C E K T years wide attention has been given the possibility of obtaining a more complete recovery of petroleum from partly depleted reservoirs by the use of surface active additives in water-flooding operations (3,16). Since their introduction, nonionic detergents have appeared to be among the most promising types of surface active additives. The number of species of various sizes produced in the reaction of a phenol with a given mole ratio of ethylene oxide may be represented by Poisson's distribution law (11, 25). Since the mole ratio of ethylene oxide can be varied continuously above a value of I, this reaction can produce detergents of any desired composition (IO). For a given phenol, the length of the polyoxyethylene chain determines the hydrophilic-lipophilic
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balance of the molecule (4). Recently, complete series of pol) oxyethylated detergents have become available in research quantities. The availability of these series permits a comprehensive investigation of the effects of hydrophilic-lipophilic balance on the displacement of petroleum from solid surfaces. The efficiencies with which these detergent solutions displace petroleum from hydrophobic sand surfaces has been investigated by a centrifugal displacement method. The ability of a detergent solution to displace petroleum from reservoir surfaces is a primary requirement if the detergent is to aid in the more complete recovery of petroleum from a reservoir that has hydrophobic surfaces. However, this may not be the only requirement, and a better displacement of petroleum m a y
