PRODUCT AND PROCESS DEVELOPMENT
Copolymers of Pyridine Analogs of Chalcone with Butadiene C. S. MARVEL, L. E. COLEMAN, JR.,
AND
GEORGE P. SCOTT
University o f Illinois, Urbana, 111.
W. K. TAFT
AND
8. G. LABBE
Government Laborofories, Universify o f Akron, Akron, Ohio
T
HE copolymerization
of benzalacetophenone with butadiene to give a low-hysteresis synthetic rubber opened up a new field of synthetic copolymers for study ( 1 0 , 1 1 ) . Recently, polymerization studies on cinnamic acid and its derivatives (9) and the furan ( 1 1 ) and thiophene analogs ( 1 8 ) of chalcone have been reported. This investigation extends this class of compounds to the pyridine analogs of chalcone and cinnamic acid. T h e preparation of these new monomers and their polymerization with isoprene and vinyl monomers have been described (8). The GR-S Mutual recipe a t 50" and 30" C. has been used t o give copolymers of 2-pyridalacetophenone(I), 2-pyridal-pchloroacetophenone(S'), 3-pyridalacetophenone(II), 4-pyridalacetophenone(III), 2-methyl-5-cinnamoylpyridine(VII), and Pcinnamoglpyridine(VII1) with butadiene. A modification of this recipe gave copolymers of 2-cinnamoylpyridine(VI) and Z-pyridal-2'-acetylpyridine(IX) with butadiene.
Four polymerization recipes
were used i n these investigations GR-S Mutual Recipe. The Mutual recipe ( 4 ) was modified t o a monomer charge of 10 grams with 20 grams of O.S.R. soap solution. Hooker's lauryl mercaptan (a mixture of primary mercaptans having an average molecular formula C12.6H26.2SH) was employed as the modifier in all of the recipes used. Azobisisobutyronitrile Recipe. This recipe was the same a8 the Mutual recipe, except that 0.02 gram of azobisisobutyronitrile was used as initiator in place of the potassium persulfate. Solution Recipe. Five-gram monomer charges were used with 0.04 gram of azobisisobutyronitrile as initiator and 10 ml. of benzene or dimethylformamide as solvent. Polymerization temperature was 60' C. Acid-Side Recipe. The recipe of Potts ( I S ) was used Kith 10 grams of monomers.
Monomers hIP-635-S Hooker's lauryl mercaptan Aaobisisobutyronitrile Water (boiled and cooled under nitrogen to eliminate oxygen)
IV. R V. R
I. R = 2-pyridyl 11. R = 3-pyridyl 111. R = 4-pyridyl
=
/I
VI. R = 2-pyridyl VII. R = 2-methyl-5-pyridyl VIII. R = 4-pyridyl
IX
T h e use of azobisisobutyronitrile as initiator in place of potassium persulfate in the Mutual recipe a t 50' C. gave sticky, lowconversion polymers in the case of pyridalacetophenones. With 2-methyl-5-cinnamoylpyridine and 44nnamoylpyridine the copolymers showed no marked difference from those obtained in the Mutual recipe. The three p-pyridalacrylic acids have been copolymerized with butadiene using the acid-side recipe a t 50" C. The incorporation of the ketone or acid was determined by nitrogen analysis of a thrice reprecipitated copolymer. Incorporation data indicate that 2-, 3 - , and 4-pyridalacetophenone enter the growing copolymer chain rapidly and may have a tendency to alternate with the butadiene units, while 2-methyl-5cinnamoylpyridine and 4-cinnamoylpyridine units enter the growing chain at a slower rate. However, no study has been made of t h e reactivity ratios of these unsaturated ketones.
214
0.176 0.3
190
NHz
= C1
0 @-CH=CH-C-R
Parts 100 10
2-Methyl-5-cinnamoylpyridine shows most promise as polymer
Copolymers of 2-Pyridalacetophenone and 2-Pyridal-pchloroacetophenone with Butadiene. Butadiene and 2-pyridalacetophenone formed copolymers in the Mutual recipe a t 50' and 30" C. with potassium persulfate initiation and a t 50' C with azobisisobutyronitrile initiation. The 9 O / l O butadieneketone copolymers prepared at 50' C. with potassium persulfate initiation were rather tough and very elastic. Increasing the ratio of ketone increased the stickiness of the copolymer. When azobisisobutyronitrile was used as initiator, a very sticky lowconversion polymer was obtained. Polymers formed a t 30" C. were also very sticky, and only low-conversion polymers were obtained. The ketone was incorporated in these butadiene copolymers in a ratio about two times that of the charge ratio. Table I shows some of these copolymers and their properties. 2-Pyridal-p-chloroacetophenone exhibited the same polymerization reactions as 2-pyridalacetophenone, although the copolymers were formed a t lower conversions and tended to be soft and sticky. Some of these copolymers are listed in Table 11. Copolymers of 3- and 4-Pyridalacetophenone with Butadiene. The 3-pyridalacetophenone-butadiene copolymers were insoluble at conversions above 40%. These raw polymers were not as tough as the 2-pyridalacetophenone-butadiene copolymers, but were more elastic. Copolymers were formed a t 50" C. using either potassium persulfate or azobisisobutyronitrile as initiator and a t 30" C. using potassium persulfate initiation in the Mutual
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 48, No. 2
PRODUCT AND PROCESS DEVELOPMENT
Table I. Copolymers of Butadiene and 2-Pyridalacetophenone Charge Ratioa 95:s 50/10
85/15
75/25 a
Modifier,
G.
0.0176 0 0176 0 0176 0 0176 0.0126 0 0176 0 0125 0 0125 0.0352 0.0352 0.0332 0 0332 0 0704 0.0704 0.0176
Time, Hr. 6 8 10 7 8 5 10
12
8 5 IO 11 12
12.5 10
(hIutua1 recipe a t 50' C.) Dilute 70 % Solution Conversion Solubility Viscosity6 38 1.51 51 1.77 95 65 90 1.45 32 55 1.52 35 55 2.08 45 95 1.94 46 95 1.91 61 55 1.72 30 33 38 42 46.6 49.5 33
98 98 97 99 98 100 80
1 14 1.45 1.52 1.71 1.92 2.10 0 70
c/c
Max. L;; Ketone 1ncorp.d
Anal.,
% N
Ketone Incorp.c
0.52 0.73 0.42 1.93 1 40 1.44 1.84 1.46
13.1 5 9 7 7 28.8 20.8 21.5 21.8 16 4
5.5 7.7 31 2 28.6 22 2 21.8 16.4
2 48 2.50 2.26 2 I5 2.04 1.95 0 70
37 0 37.3 33 8 32 0 30.5 25.0 24 5
50.0 45.5 39 6 35.8 32 4 30 4 71.3
13 1.
Butadiene-ketone.
h Determined in benzene. C
d
Calculated from conversion data and nitrogen analpsis. Calculated from conversion data and charge ratio.
Table II.
Copolymers of Butadiene and 2-Pyridal-p-chloroacetophenone
Chayge Ratioa
AIodifier, G.
Time, Hr.
90/10e 85/l5e
0 0352 0 0352 0 0352 0 0362 0.0352 0.0362
12 12
9o/ros
(Mutual recipe a t 50c and 30' C . ) Dilute 7% % Soluti,on Conversion Solubility T'iscosityb
16
50 46 60
24 36 47
12 28
10
79 27 97 95 loo 59
1.27 1,18 1.30 2.07 2 41 1.62
ilnal.,
70
70N
Ketone 1ncorp.c
Max. 70 Ketone 1ncorp.d
1.18 2.24 1.50 2.21 2.05 1.97
20.0 32 7 25.0 38 0 41.5 34 1
20.0 32.7 25.0 100 0 83.5 35 8
Butadiene-ketone. Determined in benzene. Calculated f r o m conversion d a t a and nitrogen analysis. d Calculated f r o m conversion data and charge ra.tio. e Temperature 50' C f Temperature 30" C . a
b
Table 111.
Copolymers of 3-Pyridalacetophenone and Butadiene
Charge Ratioa
hlodifier,
G.
Time, Hr.
50/10
0.0362 0,0792 0.0792 0.0792 0.0704 0.0704 0.0704 0.0704 0.0528 0.0528 0.0528
4.5 4.5 4.5 5 5 5 6 6 5 6 7
85/15
4
( M u t u a l recipe a t 50' C.) Dilute % Yo Solution Conversion Solubility Viscosityb 35 50 1.35 31 82 2.72 32 88 2.94 31 97 2.75 33 73 1.90 36 85 2.45 38 46 1.67 48 65 1.98 39 40 1.13 50 50 1,27 56 32 0.78
Anal.,
yo N
1.35 1.15 1.06 1 15 1.24 1.08 1.02 1.67 1 63 2 21 1.30
%
Ketone 1ncorp.c 21 17.3 15.9 17.3 18.5 16.5 15.8 20.8 24.2 30.0 19.5
Max. 7% Ketone 1ncorp.d 28.6 31.8 31.8 31 8 30 2 27 8 26 3 20 8 38.6 30 0 26 8
Butadiene-ketone. Determined in benzene. Calculated from conversion d a t a and nitrogen analysis. d Calculated f r o m coni-ersion d a t a and charge ratio.
a b
Table IV. ChaFge Ratioa
Modifier,
90/10
0 0352 0.0704
a
G.
Copolymers of 4-Pyridalacetophenone and Butadiene Time, Hr. 4 0
(Mutual recipe a t 50' C.) Dilute % 7 Solution Conversion Solubillty Viscosityb 46 34 0.35 57 32 0.60
7% Anal.,
Ketone
% K
1ncorp.c
1 82 1.52
21.6 17.5
Max. yG Ketone 1ncorp.d 21.6 17.5
Butadiene-ketone.
b Determined in benzene. d
February 1956
Calculated from conversion data and nitrogen analysis. Calculated from conversion d a t a a n d charge ratio.
INDUSTRIAL AND ENGINEERING CHEMISTRY
215
PRODUCT AND PROCESS DEVELOPMENT charged in the preparation mixture. The polymers prepared a t 30" C. in the Mutual recipe were formed in low conversion and were sticky and had little snap. Initiation with azobisisobutyronitrile a t 50" C. gave polymers which appeared to be almost identical with those formed by potassium persulfate initiation in the Mutual recipe. I n the case of the pyridalacetophenones, the conversions were much lower, and the polymers were unattractive. Some of these copolymers are listed in Table 1-1. Copolymers of Other Pyridine Analogs of Chalcone with Butadiene. 2-Pyridal-p-aminoacetophenone (IV) has been found to retard but not inhibit butadiene polymerization, when the Mutual recipe is used. No other reactions were attempted with this monomer. The dimer of 2-pyridine aldehyde (6, 7') (X) acted as a poll,merization inhibitor with butadiene, when the Mutual recipe was used. No polymer could be isolated after 4 days. S o further work was done with this compound. %Cinnamoylpyridine(VI) and 2-pyridal-2'-acetylpyridine( I X ) were very similar in their polymerization reactions. These ketones did not form copolymers with butadiene a t polynicrization times less than 17 hours, when the Mutual recipe a a s used a t 50' C. However, after 3 days and with twice the usual amount of soap solution, low-conversion copolymers were obtained. Copolymers of Pyridine Analogs of Cinnamic Acid with Butadiene. The pyridine analogs of cinnamic acid were studied briefly. The Mutual recipe a t 50' C. was unsatisfactory with either azobisisobutyronitrile or potassium persulfate initiation. The in-
recipe. If charges containing more than 15 to 20% ketone were used, some crystalline monomer remained in the latex, These copolymers are also shown in Table 111. All of the 4-pyridalacetophenone-butadiene copolymers prepared had very high gel content and in general this ketone gave no improvement over the other monomers. Some of these polymers are listed in Table IV. Copolymers of 4-Cinnamoylpyridine with Butadiene. Polymers were prepared in the Mutual recipe at 30' and 50' C. The dilute solution viscosities were very good, and the polymers were soluble in benzene. Because of the small amount of monomer prepared, only a few butadiene copolymers were prepared; but they were similar to the 2-methyl-5-cinnamoylpyridinebutadiene copolymers and deserve further investigation as low temperature, low-hysteresis, and oil-resistant rubbers. These polymers are described in Table V. Copolymers of 2-Methyl-5-cinnamoylpyridhe with Butadiene. 2-Methyl-5-cinnamoylpyridine shows the most promise as a monomer. Several butadiene ropolymers were prepared using t h e Mutual recipe at 30' and 50" C. with potassium persulfate initiation and at 50' C. with azobisisobutyronitrile initiation. 'The 50" C. Mutual recipe using potassium persulfate gave the most interesting polymers. Good emulsions were obtained when as much as 257, ketone was used in the charging stock; above this ratio, some crystalline monomer remained in the latex, The polymers became stickier as the amount of ketone was increased. This ketone was generally incorporated in the same ratio as
Table V. Polymer
Copolymers of 4-Cinnamoylpyridine and Butadiene Charge Ratioa 90/10 90/10 QO/lO 90/10 90/10 90/1o
NO.
2-27-20 2-27-3c 2-27-4C 2-4-3d 2-4-4d 2-32-3e
Modifier,
0.
0 0352 0 0352 0 0352 0 0352 0 0362 0 0362
Time, Hr. 3 5
6 10 11 24
%
Conversion 20 0 34 0 39 5 76 0 83 22
%
Solubility 100 100 100 100 90 50
Dilute Solution Viscosity b 2 94 2 98 2 60 1 38 1 30 1 73
a Butadiene-ketone. b Determined in benzene. C
Polymerization temperature 50' C.
d Polymerization temperature 52' C.
* Polymerization
Table VI. Charge Ratioa 90/10e
85/156
80/20e 90/101
temperature 30" C.
Copolymers of 2-Methyl-5-Cinnamoylpyridine with Butadiene
Modifier,
G.
0.0176 0.0176 0.0176 0,0176 0.0176 0.0176 0.0176 0.0176 0.0176 0.0352 0.0440 0.0440 0.0176 0.0352 0.0352 0.0176 0.0352 0.0352 0.0528 0.0704 0.0352 0.0352 0,0704 0.0352
Time, Hr. 5 6 7 R
9 9 10
10 6 7 7.5 7.5 8 11 12 8 30 36 40 40 45 45 45 50
Dilute % Solution % . Conversion Solubilityb Viscosityb 39 100 1.87 44 100 1.88 49 100 1.72 58 1.52 100 95 68 1.25 77 90 1.10 72 95 1.20 1.02 95 77 46 100 1.63 44 100 3.00 2.92 56 100 56 100 3.10 62 100 1.51 75 97 1.16 80 1.00 98 60 100 1.37 32 2.89 40 100 g8 3.94 37 3.80 46 loo 3.26 100 60 3.29 53 loo 2.07 93 3.20 50 59 100 loo 3.35
Anal.,
%N 0.89
0.89 0.80 0.76 0.66 0.67 0.71 0.56 0.99 1.30
0.88
0.87 0.82 0.97 0.96 1.25 0.60 1.02 1.08 1.14
0.85 0.60 1.04 0.56
%
Ketone Incorp. 13 4 12.9 12.0 11.2 10.1 10.1 10.8 10 1 15.0 21 .o 14 05 13 9 12.0 15.5 15 3 19 0
9.0
16.2 17.0 18.0 15.0 9.1 16.5 15.0
Max.
Ketone 1ncorp.d 25 6 22 8 20.4 17 3 14.7 13.0 13.9 13.0 32.6 34.5 27.8 27.8 24.2 20.0 18.8 33.3 31.2 25.0 27.0 21.8 16.7 18.8 20.0 16.9
a Butadiene-ketone. b Determined in benzene C
Calculated from conversion d a t a and nitrogen analysis.
d Calculated from conversion d a t a a n d charge ratio.
Mutual recipe a t 50° C. I Mutual recipe a t 30' C. 6
216
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 48, No. 2
PRODUCT AND PROCESS DEVELOPMENT
Table VII.
Copolymers of /3-(Pyridyl)-acrylic Acids and Butadiene" (Acid-side recipe at 50' C.)
Polymer NO.
Table VIII.
%
Time,
Charge Ratioh
Hr.
Isomer0
Conversion
Dilute Solution Viscosityd
Description of Evaluation Samples and Controls X-720
332
Comonomers with butadiene
Styrene
2-Pyridalacetophenone
Monomer ratio in charge Conversion, yo Time, hours Temp. of polymerization, C Formula Combined comonomer, % ' Gel Dilute solution viscosity Mooney viscosity (ML-4 a t 212O F.)
71/29
a
"r,
Solubilityd
85/ 15 42 12 50 Mutual 25 10 2.23 115
50 Mutual 3 2,lb 48
Illinoie Samples 336 337 3-Pyridyl2- Me thyl-5cinnamoylacetophenone pyridine 85/15 90/10 56 31.5 7.5 4.5 50 50 Mutual Mutual 14 17 3 30 3,18 2.58 145 > 136
34Za 2-Methyl-5cinnamoylpyridine 85/15 49 6 50 Mutual 15 1 2.08 52
Prepared by John H. Rassweiler.
solubility of these acids was an important factor in the polymerization. The compounds were insoluble in all of the common solvents and only slightly soluble in dimethylformamide thus limiting solution polymerization. Bulk recipes were impractical because of the high melting points of the monomers. I n emulsions systems, the acid-side recipe was the only one in which polynierization occurred: the acid remained at the bottom of the vesqel if charged in concentrations greater than 5%. The butadiene copolymers of the 3- , and 4-pyridylacrylic acids were white, with good tack and fair elasticity. The p-( 2-p) ridy1)-acrylic acid-butadiene copolymers were low-conversion oils (Table VII). The rate of polymerization was in the decreasing order 4-isomer > 3- isomer >> 2- isomer. Further investigation of the polymerization system and the 3- , 4-isomers would probably give interesting polymers, as these compounds are actually aniino acids. These copolymers are listed in Table VII.
The recipes for Perbunan 18 (tread-type recipe) differed from the above as follows: sulfur, 1.75 grams; 2,2'-dithiobisbensothiazole, 0.90 grams; and stearic acid, 1.50 grams. Evaluation of Illinois sample 332 [butadiene(85)-2-pyridalacetophenone( l5)] indicated that it is a high viscosity polymer with good tensile properties and extremely high modulus when mixed in the tread-type recipe. The oil resistance is moderately good, but unfortunately the low temperature flexibility is poor. Stress-strain properties are similar t o GR-S in the carcass-type recipe, but the temperature-rise values and set values are high. The copolymer made from butadiene( 85)-2-methyl-5-cinnamoylpyridine( 15) was compounded and evaluated as Illinois sample 336. This polymer had a high Mooney viscosity, which may account for the high modulus and low elongation of the tread-type stocks, although per cent set values indicate faster curing for this polymer than for standard GR-S. The low temperature flexibility is better than for GR-S, and the polymer had little tendency to crystallize. The oil resistance is better than
Three types of butadiene copolymers were evaluated as rubbers
Samples of some butadiene-2-pj ridalacetophenone, butadiene-3-pyridalacetophenone, and butadiene-2-methyl-5-cinnamoylpyridine copolymers have been evaluated a s rubbers (Tables VI11 t o X I I I ) . They were compounded in the treadtype and carcass-type recipes given below, and the stress-strain ( 5 ) ,low temperature ( S ) , oil resistance ( I ) , and hysteresis properties ( 2 ) were determined on the vulcanizates by standard testing procedures.
Carcass Stock Recipe
Tread Stock Recipe Polymer E P C black Zinc oxide Sulfur 2,2'-Dithiobisbenzothiazole
February 1956
Parts 100 40 5 2 1. 7 5
Polymer H M F black
PbsOa
Sulfur
Z,Z'-Dithiobisbenzothiazole Circosol-2XH
Parta 100 30 2.5 2 1 20
Table IX.
300% modulus, lb./sq. inch Tensile strength, lb./sq. inch Elongation, % Set, %
Stress-Strain Data at
(Tread-type recipe) Min. PerCured &t Xbunan 292' C. 720 18 25 480 1660 50 1040 2050 100 1520 2280 25 2310 2990 50 3810 3520 100 3640 2940 25 810 490 50 650 450 100 500 370 25 25 11 50 17 10 100 10 7
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
Ill. 332 3080 2940 2830
77" F. Ill. 336 2960
.. ..
Ill. 337
., .. ..
Ill. 342 2030 2270
..
4210 3110 2910 3200 3960 2610 2930 2780 3870 2620 2880 2300 390 310 280 420 390 240 270 340 390 250 250 260 20 2 3 10 19 2 3 7 2 0 2 3 4
217
PRODUCT AND PROCESS DEVELOPMENT Gehman low Temperature Data
Table X.
(Tread-type recipe) Perbunan Ill. 18 332
X720 Rlin. cured a t 292' F. Temp., 65 60 55 60 45 40 35 30 25 20 15 10 5 0 25
- O
60
50
50
C.
4 6 38 111 138 148 153 ,
3
4
7 8 9 12 16 25 42 70
4 7 40 93 119 130 137 143
,.
...
164 167
Ill. 336
148 I58
342 Ill.
50
50
50
2 6 22 75 118 131 138 142
3 6 25 67 96 117 124 134 139
6 20 62 98 112 130 135 141
147 151
147 153
, ,
114 148
Ill. 337
.
,..
...
155 155
GR-S, although not as good as Perbunan 18. In a carcass-type recipe the temperature-rise properties of polymer 336 were exceptionally low and, although the modulus was high and the tensile strength and per cent set xere loa-, it appeared that this polymer could be of value in a carcass-type compound. Consequentlj-, polymer 342 was made similar t'o KO,336 but of a more normal viscosity; when tested for temperature rise it produced values of normal magnitude, on the order of those obtained with GK-S. Illinois polymer 342, similar to 336 except that, it was made to a viscosity of 52 hIL-4, produced properties like those of 336 but had better elongation, as might be expected because of the difference in viscosit,y. The temperature-rise properties are mentioned above. Illinois sample 33i, a copolymer made from butadiene( 90)-3pyridaiacetophenone(lO), produced vulcanizates similar to those of polymer 336. Summary
Gage, inch
0 074
0.080
0 079
0.078
0 080
0 074
Oil Resistance Data
Table XI.
(7 day immersion a t 77' F.
Tread-type recipe) Volume Increase, 76
x-
Perbunan 18 26
720 Oil 1 2 3 l0OY0 iso-octane 60/40 iso-octanetoluene Special solventQ e
Ill. 332
Ill. 336
Ill. 337
Ill. 342
16 33 125 82
6 9 16 23
0 6 9 9
6 9 48 44
6 16 69 52
13 16 60 44
16 30 86 52
224 218
100 95
69 69
130 135
125 125
120 120
135 130
Composed of 15% xylene, 20% toluene, 5% benzene, 60% iso-octane.
Stress-Strain at
Table XII.
77' F.
(Carcass-type recipe) Min. Cured a t 280° F. 300% modulus, lb./sq. inch
20 40 80
Tensile strength, Ib./sq. inch
20 40 80 20 40 80 20 40 80
Elongation,
%
Set, %
X-
720 230 450 630 1650 1890 1460 950 650 490 33 18 5
Table XIII.
Ill. 332
111. 336
Ill. 337
Ill. 342
260
690 960 1100 1520 1190 1270 470 330 330 4 1 1
590 640 630
110 380 450 1190 1120 1160 740 580 500 16 5
280
400 1420 1550 960 840 780 570 13 1;
Initial compression,
YO
Temperature rise,
F.
Set, %
3
Goodrich Hysteresis Data
(Carcass-type recipe) Min. Ill. Cured a t X332 280O F. 720 Shore -4hardness
1190 I050 1020 450 410 390 2 1 1
60 90 120 60 90 120 60 90 120 60 90 120
49 39 40 32.0 30.2 31.4 29 25 25
35 35 37 45.5 45.3 44.1 116 127 100
Ill. 336 46 47
41 41
24 4 24.0
29.8 28.4
12 11
23 20
f::: y : : 8.1
46.6
Ill. 337
z:;
111. 342 39 40 39 34.1 32.1 33.0 24 22 24
'i;:
A series of pyridine analogs of chalcone and cinnamic acid has been copolymerized nith butadiene. This series includes 2-p>ridalacetophenone, 2-pyridai-p-chloroacetophenone, 3-pyridalacetophenone, 4-pyiidalacetophenone, 2-cinnamoylpyridine, Z-methyl-5-cinnamoylpyridine,4-cinnamoylpyridine, and 2pyridal-2'-acetylpyridine. Butadiene and 2-pyridal-p-aminoacetophenone did not form a copolrmer. The copolymers of 2-pyridalacetophenone, 3-pyridalacetophenone, and 2-methyl5-cinnamo~lpyridine R ith butadiene have been evaluated; the 2-methyl-5cinnamoylpyridinecopolymer shom s some promise as a new synthetic rubber w-ith low heat build-up properties. Acknowledgment
The work discussed herein was performed as a part of the research project sponsored by the Federal Facilities Corp., Office of Synthetic Rubber, in connection with the government s?-nthet,icrubber program. The authors are indebted to Stanley Detrick, E. I. dn Pont de Kemours & Co., for the emulsifier, MP-635-S. Its percentage composition is as follows: Sodium alkanesulfonates in Ci8 range Unreacted hydrocarbon Sodium chloride Sodium sulfate Balance, water and about 370 isopropyl alcohol
Literature cited (1) Am. Soc. Testing Materials. Philadelphia, Pa., ASTM Designa-
tion D 471-43T. ( 2 ) Ibid., D 6 2 3 4 1 T , Nethod A . (3) Ibid., D 1053-52T. (4)Frank, R. L., ildams, C. E., Blegen, J. R., Deanin, R., and Smith, P. V., J r . , IXD.ESG. CHERI.39, 887, 893 (1947). (5) Garvey, B. S., Jr., Ibid.,34, 1320 (1942). (6) Hensel, H. R., Angew;. Chem. 65, 491 (1953). (7) Kramer, F., and Krum, IT.,Bey. 86, 1.586 (1953). (8) Marvel, C. S.,Coleman, L. E., Jr., and Scott, G. P., J. 0 7 0 . Chem., in press. (9) Marvel, C. S., RIcCain, G . H., and Passer, M., IND. ENG.CHCM. 45, 2311 (1953). (10) Marvel, C. S.,McCorkle, J. E., Fukuto, T. R., and "right, J. C., J. Polvmer Sci. 6 , 766 (1951). (11) Rlarrel, C. 9 . . Peterson, IT. R . , Inskip, H. IC., NcCorkle, J. E., Taft, W. K., and Labbe, B. G., IND.ENG.CHEm 45, 1532 (1953). (12) Marvel, C. S., Quinn, J . AI., and Showell, J. S., J.Org. Chem. 18, 1730 (1953). (13) Potts, R., University of Illinois, private communication.
8.0
RECEIVED for review .4ugust 18, 1956.
218
49.5 10.3 0.86 0.4
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
ACCEPTED
Sovember 30, 1955.
Vol. 48,No. 2
