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Synthesis of new plasticizers from naphthenic acids of kerosine fractions
SleN'I'HESI_S OF NEW PLASTICIZERS FROM NAPHTHENIC ACIDS OF KEROSINE FRACTIONS* SHAMKHAL MAMEDOV, A. S. RZAYEV a n d I. L. N I Z K E R Institute of Petroleum Chemical Processes, Az. S.S.R. Academy of Sciences
(Received 31 March 1962)
THE current task of petroleum chemistry is the development of new routes for the synthesis of esters used as solvents and plasticizers. A m~rked increase in the production of polymers involves a growth in the requirements for plasticizers improving the use properties of articles made from polymeric products. Many types of articles based on synthetic polymers cannot be made at all without p]asticizers [1]. In industry, widely used methods for the synthesis of esters are the esterification of acids and anhydrides with mono- and polyhydric alcohols [2] and the condensation of acids with ethylene oxide [3]. Esters may also be obtained by the reaction of halogen derivatives with alkali-metal salts of organic acids. Meyer [4], and then Engelhardt [5], heated a mixture of dichloroethane and sodinm acetate under pressure (20-22 arm) at a temperature of 180-200 ° and obtained the full glycol ester of acetic acid. Ayres and Haabestad [6] heated a mixture of dich]oroethane and the sodium salt of stearic acid under a pressure of 18-20 atm at 150-160 ° and obtained ethylene glycol stearate. It can be seen from this that the synthesis of such esters is limited by the supply of raw material and the complication of industrial processes associated with the use of pressure. It is therefore important to devise new industrial processes for the mass production of high-quality and cheap articles based on polymeric products. In view of this it is of great interest to bring into the plasticizer industry the considerable resources of naphthcnic acids forming by-products in the processing of petroleum and petroleum products, which are mainly used in the soap industry. The amount of naphthenic acids isolated from Baku, Turkoman, and Volga oils is quite considerable. Thus, for example, the content of naphthenic acids in Baku oils amounts to 0.5-1.8%. We have developed a simple method for the synthesis of glycol esters of naphthenic acids [7] using dichloroethane and by-passing scarce ethylene * Neftekl~imiya 2, No. 5, 788-792, 1962. 504
New plasticizers from kerosine naphthenic acids
505
glycol. The synthesis is based on the reaction of diehloroethane with the sodium ~ l t s of the naphthenic acids at 170-190 ° and atmospheric pressure according to the scheme: CHzC1 NaOOCR CHaOOCR C~H2C1+ NaOOCR--~~H~OOCR + 2NaCI where R is a naphthenic radical (tool. wt. 140-160) corresponding to fivemembered monocyclic naphthenic hydrocarbons. The crude naphthenic acids of the kerosine fraction ("acidor') are subjected to prellmiuary distillation into fractions boiling at 110-140 ° and 140-160°/1-5 ram. The 110-140 ° fraction with an acid number of ~300 amounts to 55-60~, and the 140-160 ° fraction with an acid number ~280-270 amounts to 25-30~; the two fractions are esterified separately. In order to obtain the sodium salts, the acidol is neutralized with solid caustic soda at 50-100 °. By gradually raising the temperature to 170-190 °, the water formed is driven off. At this trmperature, dichloroethane is added to the mixture and reacts with the sodium salts of the naphthenic acids giving the corresponding esters. It must be noted that when the acidol is neutralized with an equivalent amount of caustic soda the dichloroethane does not react with the anhydrous salts of the naphthenic acids even at 240-250 °. However, it is sufficient to add 10~ of the initial acidol or 5 - 8 ~ of the previously prepared glycol of the naphthenic acids to the reaction mixture for the reaction between the dichloroethane and the sodium naphthenates to ccmmence. It is preferable to add the pre-formed naphthenic acid esters to the reaction mixture, since in this case the acid number of the crude plasticizer does not exceed 10-12, which facilitates the subsequent removal of the free acids by treating the raw material with 3 - 5 ~ caustic soda. The reaction between dichloroethane and the sodium naphthenates is exothermic and the temperature in the reactor may rise to 240 °, depending on the rate of addition of dichloroethane. The end of the reaction is found from the content of sodium naphthenate in a sample. The glycol esters of the naphthenic acids obtained by this method have been tested under the provisional designation "ANAZ" as a plasticizer in various polymer products. The phyaicochemical properties of "ANAZ" plasticizer. It is a high-boiling pale yellow oily liquid with a faint characteristic odour. It dissolves in almost all organic solvents and dissolves many synthetic resins forming homogeneous mixtures. The results of tests have shown that "ANAZ" plasticizer, thanks to its good compatibility with nitrocellulose, does not exude from the surface of a film at low or high temperatures, i.e. it does not "sweat" (Table 1). Use of "ANAZ". A test of the new plasticizer showed that it can be used
506
SH~m
M~mDOV e~0g.
T A B L E 1. I~HYSICOCHEMICAL PROPERTIES OF SOME PLASTICIZERS
d20 4
Name
"ANAZ " t0004~ 1900260[5 Dibutyl phthalate 278 339 Dioctyl 390 phthalate Dibutyl sebacate 314 344-5 Tricresyl phosphate 368 280/20 Trihexyl phosphate 350. 214-277/20 Castor oil ~ 900 --
--55
180
0-996
1-475 2700280 0-09
--35
175
1.048
1-4926
20O
0.982
!80
0.935
1.4891 240 -
~
230
1"170
1.5540
0.15
240
0-941 0.964
ks
35 -- 60
0.8 282-292 0-55
1!76-181
O.2
successfully [8]i Nitrolinoleum was made from collodion and " A N A Z " . :, tests showed that it completely fldfiUed the requirements of the GOST [St a~e Standard]. The nitrolinoleum based on " A N A z " was prepared b y the usual method and samples containing different a m o u n t s .of plasticizer were tested. The best results were obtained when 5 - 7 % of "ANAZ" was added to the collodion together with dibutyl phthalate. "ANAZ" m a y also be used successfully for the manufacture of plasticized rubber based on butadiene-nitryl rubber and "nairit" [9J; the results of the tests are given in Table 2 . . . . In the rubber based on butadiene-nitryl rubber a n d nairit, "ANAZ'," was tested in comparison with dibutyl phthalate and dibutyl sebaca~:*, High q u a l i t y paint-materials can be obtained from "ANAZ" plasticizer [10], for example nitro-enamel 507, in which it has successfully repla0ed castor oil. In their low degree of sweating, coatings made with "ANAZ" are superior to standar d coatings. "Perehlorovinyl" enamels made with the addition of "ANAZ" have also been investigated, in comparison with enamels prepared with tricresyl phosphate [1!]. The coating containing "ANAZ" are not inferior in their properties to the coatings with tricresyl phosphate, and have even better resistance to ageing. * The tests were carried out in ~heScientific Research Institute of the Rubber Industry (Moscow).
New plast~cizers f r m ~ k e r ~ , e naphthenie acids
507
TABLE 2.~RESULTSOF TESTSOF PLASTICIZEDRUBBER
]
Amount of plas-
t
4
tielzer, l~Iame of plasticizer
Relative Residue elonga- elonga tion, % tion, %
]byKar-
parts by weight per 100 parts of rubber
r rer's / method
•
Coefieient of frost resistanee at --25 ° I¸
•
SKN-26 Control mixture (without plasticizer) Dibutylphthalate
"ANAZ"
10 20 30
74 66 61 55
0-10 0.23 0.32 0.44
281 312 281 207
469 583 670 692
12 13 19 21
0.20 0-24 0.31 0-32
10 20 3O
64 58 53
0.25 0-35 0.42
283 256.5 218
551.5 646.7 689.5
12.1 14.0 15.0
0.33 0.41 0.51
154 128 133 113 126 119 11 L
488 566 616 620 718 626 646
8 11.2 14 14 13.6 8"8 11.2
0.21
"Nairit" Control mixture (without plasticizer) Dibutylphthalate "ANAZ"
m
10 20 30 I0 20 • 30 -
68 65 60 53 53 53 47
0.57 0.48 0.55 0.65 0.61 0.69 0.73
0.48 0-45 0.54
Samples o f d e r m a t i n [leatherette] in which t h e c a s t o r oil h a d been comp l e t e l y replaced b y " A N A Z " showed t h a t t h e latter, p r e p a r e d from n a p h t h e n i c acid fractions, is a high-quality plasticizer for this product. P r o d u c t s with different plasticizing properties c a n be o b t a i n e d according to t h e fractional composition o f the initial n a p h t h e n i c acids. T h e tests in the p r o d u c t i o n o f d e r m a t i n o f t h r e e samples o f this plasticizer synthesized f r o m t h r e e different fractions o f kerosine acidol were carried o u t o n the individual fractions o f " A N A Z " a n d on m i x t u r e s o f t h e m . T h e articles p r e p a r e d with " A N A Z " possessed good frost resistance. Table 3 gives t h e physicochemical characteristics o f the " A N A Z " fractions a n d t h e i r miscibility with various solvents. Because " A N A Z " is o n l y slight]y coloured it can be used to m a k e d e r m a t i n s o f pale shades, as has been confirmed b y trials. " A N A Z " as su¢h a n d in t h e f o r m o f films possesses a v e r y low volatility, good light-resistance, insolubility in water, stabilitY t o h e a t a n d cold, t h e
SHA~lrHALMAMBDOVe~ a/.
508
TABLE 3. PHYSICOCHEMICALCHARACTERISTICSOF "ANAZ" FRACTION8 Properties of the "ANAZ" fraction B. p., oc/3 nun H g
Solidification point, °C Acid number Saponification number Volatility a~ I~;0° Viscosity in the Ford-Engler apparatus at 20 °, see Viscosity according to Engler at 20 ° at 100 ° Miscibility: alcohol 1:1 gasoline 1:1 ethylacetate 1:1 castor oil 1:1 oxidized cotton seed oil water Odour Colour
Sample 1
Sample 2
Sample 3
190-240 -65
205-250 -58
0-994
0-998
0.34 291 "8 1.474 0.044
0.46 250.1 1.480 0-9
220-260 -40 1.002 0.42 249.6 1.481 0.068
Miffiture 3.5:3:1 190-260 -55 0.996
0"37 276.5 1"476
10
12
5.78
10.5 1-73
1"53
Miscible
60% separates out Miscible
Miscible
Immiscible Weak Pale yellow Light yellow I
absence o f t o x i c i t y , good c o m p a t i b i l i t y with film-forming agents a n d solvents, and a low solidification point, as can be clearly seen f r o m t h e Tables given. D e r m a t i n p r e p a r e d with " A N A Z " is n o t sticky a n d can be f o r m e d into rolls i m m e d i a t e l y a f t e r m a n u f a c t u r e . T h e samples o f d e r m a t i n m a d e were k e p t a t 70 ° for 8 h r in folded f o r m u n d e r a load o f 1 kg. T h e plasticizer did n o t s w e a t u n d e r these conditions.
EXPERIMENTAL 1200 g o f distilled naphthenic acids f r o m a kerosine fraction boiling within the r a n g e f r o m 115 to 140°/3ram H g a n d h a v i n g a n acid n u m b e r o f 295 was placed in a 3-1itre t h r e e - n e c k e d flask fitted with a mechanical stirrer, a reflux condenser with a w a t e r - s e p a r a t o r (of t h e D e a n a n d S t a r k t y p e ) , a d r o p p i n g funnel, a n d a t h e r m o m e t e r . T h e flask was h e a t e d t o 50 ° a n d 318 g o f p o w d e r e d caustic soda was a d d e d in portions o v e r 2 hr with continuous s~irring; its a d d i t i o n was c o m p l e t e d a t 100 °, a f t e r which, t o r e m o v e t h e w a t e r formed, the t e m p e r a t u r e o f the r e a c t i o n m i x t u r e was slowly raised. Elimination o f the w a t e r was completed a t 195-200 °. T h e t o t a l a m o u n t o f distillate
New plasticizers from kerosine naphthenic acids
509
obtained was ~140 ml. With the reaction mixture at 195-200 °, dichloroethane was added in drops from the dropping funnel. The dichlorocthane which had not reacted, on evaporating off, was condensed in the condenser and ran into the water-separator where it was separated from the water and drawn off through a cock. After sore9 time, when the evolution of water had ceased, the dichloroethane in the form of an azeetropie mixture running from the condenser was returned to the reaction flask. As the dichloroethane was added the reaction mixture became more mobile and sodium chloride separated. I n all, ~650 g of dichloroethane was added of which ~400 g reacted. The esterification process can be carried out in 6-8 hr. The reaction mixture was cooled to 50-60 °, 250-300 ml of water was added and the lower aqueous salt layer was separated from the upper layer. The upper layer was washed with water and after settling was distilled in a vacuum of 1 mm Hg. The yields of the fractions were as follows: I (100-185°) II (185-200°) III (200-240°) Residuo
-- 60 g; -- 170 g; --910 g; -- 50 g.
Fraction I I I consisted of the finished "ANAZ" plasticizer: yield 76o/0. For properties see Table 1. SUMMARY
1. A method for obtaining glycol esters of naphthenic acids has been developed and the applicability of this method for the production of glycol esters of other acids has been established. 2. The plasticizing and other properties of the plasticizer "ANAZ" [glycol esters of naphthenic acids] in rubber, nitrocellulose, perchlorinated vinyl resins, and polyvinyl and nitrocellulose compositions has been studied. The results of the trials have shown its excellent plasticizing properties and complete suitability for use. Translated by
B . J. H A Z Z A R D
REFERENCES
1. A. Ya. DRINBERG, Tekhnologiya plenkoobrazuyushchikh veshchestv. (Technology of Film-forming Substances.) Goskhimizdat, Leningrad and Moscow, p. 96, 1955 2. C. ELLIS, Khimiya uglevodorodov nefti i ikh proizvodnykh. (Chemistry of the Hydrocarbons of Petroleltrn and Their Derivatives.) United Scientific and Technical Pub]ishing House, Moscow, p. 562, 1938 3. C. Wt~RTZ, Ann. 116, 249, 1860; Ann. 113, 255, 1860 4. K. H. MEYER, German Pat. 332,677, 1919; Chem. Zbl. II, 646, 1921 5. A. ENGELHARDT, German Pat. 404,999, 1919; Chem Zbl. B 1, 1529, 1925
510
SHAMKHALMAMEDOVet al.
6. E. E. AYRES and E. H. HAABESTAD, Canad. Pat. 286,077, 1929; Chem. Abstr. 28, 1417, 1929 7. SHAMIKHAL MAMEDOV, R. R. PASHAYEV, I. L. NIZKER and A. S. RZAYEV, U.S.S.R. Authors' Certificate ] 14,337, 1958 8. SHAMKHAL MAMEDOV, A. S. RZAYEV and I. L. NIZKER, Khim. prom. ~o. 7, 26, 1960 9. SHAMKHAL MAMEDOV, A. S. NOVIKOV. G. V. DOROKHINA, A. S. RZAYEV and I. L. NIZKER, U.S.S.R. Authors' Certificate 132,803, 1960 10. SHAMKHAL MAMEDOV, A. S. RZAYEV and I. L. NIZKER, U.S.S.R. Authors' Certificate 124,573, 1959 11. SHAMKHAL MAMEDOV, I. L. NIZKER and A. S. RZAYEV, U.S.S.R. Authors' Certificate 124,574, 1959
(Received 31 March 1962)
THE current task of petroleum chemistry is the development of new routes for the synthesis of esters used as solvents and plasticizers. A m~rked increase in the production of polymers involves a growth in the requirements for plasticizers improving the use properties of articles made from polymeric products. Many types of articles based on synthetic polymers cannot be made at all without p]asticizers [1]. In industry, widely used methods for the synthesis of esters are the esterification of acids and anhydrides with mono- and polyhydric alcohols [2] and the condensation of acids with ethylene oxide [3]. Esters may also be obtained by the reaction of halogen derivatives with alkali-metal salts of organic acids. Meyer [4], and then Engelhardt [5], heated a mixture of dichloroethane and sodinm acetate under pressure (20-22 arm) at a temperature of 180-200 ° and obtained the full glycol ester of acetic acid. Ayres and Haabestad [6] heated a mixture of dich]oroethane and the sodium salt of stearic acid under a pressure of 18-20 atm at 150-160 ° and obtained ethylene glycol stearate. It can be seen from this that the synthesis of such esters is limited by the supply of raw material and the complication of industrial processes associated with the use of pressure. It is therefore important to devise new industrial processes for the mass production of high-quality and cheap articles based on polymeric products. In view of this it is of great interest to bring into the plasticizer industry the considerable resources of naphthcnic acids forming by-products in the processing of petroleum and petroleum products, which are mainly used in the soap industry. The amount of naphthenic acids isolated from Baku, Turkoman, and Volga oils is quite considerable. Thus, for example, the content of naphthenic acids in Baku oils amounts to 0.5-1.8%. We have developed a simple method for the synthesis of glycol esters of naphthenic acids [7] using dichloroethane and by-passing scarce ethylene * Neftekl~imiya 2, No. 5, 788-792, 1962. 504
New plasticizers from kerosine naphthenic acids
505
glycol. The synthesis is based on the reaction of diehloroethane with the sodium ~ l t s of the naphthenic acids at 170-190 ° and atmospheric pressure according to the scheme: CHzC1 NaOOCR CHaOOCR C~H2C1+ NaOOCR--~~H~OOCR + 2NaCI where R is a naphthenic radical (tool. wt. 140-160) corresponding to fivemembered monocyclic naphthenic hydrocarbons. The crude naphthenic acids of the kerosine fraction ("acidor') are subjected to prellmiuary distillation into fractions boiling at 110-140 ° and 140-160°/1-5 ram. The 110-140 ° fraction with an acid number of ~300 amounts to 55-60~, and the 140-160 ° fraction with an acid number ~280-270 amounts to 25-30~; the two fractions are esterified separately. In order to obtain the sodium salts, the acidol is neutralized with solid caustic soda at 50-100 °. By gradually raising the temperature to 170-190 °, the water formed is driven off. At this trmperature, dichloroethane is added to the mixture and reacts with the sodium salts of the naphthenic acids giving the corresponding esters. It must be noted that when the acidol is neutralized with an equivalent amount of caustic soda the dichloroethane does not react with the anhydrous salts of the naphthenic acids even at 240-250 °. However, it is sufficient to add 10~ of the initial acidol or 5 - 8 ~ of the previously prepared glycol of the naphthenic acids to the reaction mixture for the reaction between the dichloroethane and the sodium naphthenates to ccmmence. It is preferable to add the pre-formed naphthenic acid esters to the reaction mixture, since in this case the acid number of the crude plasticizer does not exceed 10-12, which facilitates the subsequent removal of the free acids by treating the raw material with 3 - 5 ~ caustic soda. The reaction between dichloroethane and the sodium naphthenates is exothermic and the temperature in the reactor may rise to 240 °, depending on the rate of addition of dichloroethane. The end of the reaction is found from the content of sodium naphthenate in a sample. The glycol esters of the naphthenic acids obtained by this method have been tested under the provisional designation "ANAZ" as a plasticizer in various polymer products. The phyaicochemical properties of "ANAZ" plasticizer. It is a high-boiling pale yellow oily liquid with a faint characteristic odour. It dissolves in almost all organic solvents and dissolves many synthetic resins forming homogeneous mixtures. The results of tests have shown that "ANAZ" plasticizer, thanks to its good compatibility with nitrocellulose, does not exude from the surface of a film at low or high temperatures, i.e. it does not "sweat" (Table 1). Use of "ANAZ". A test of the new plasticizer showed that it can be used
506
SH~m
M~mDOV e~0g.
T A B L E 1. I~HYSICOCHEMICAL PROPERTIES OF SOME PLASTICIZERS
d20 4
Name
"ANAZ " t0004~ 1900260[5 Dibutyl phthalate 278 339 Dioctyl 390 phthalate Dibutyl sebacate 314 344-5 Tricresyl phosphate 368 280/20 Trihexyl phosphate 350. 214-277/20 Castor oil ~ 900 --
--55
180
0-996
1-475 2700280 0-09
--35
175
1.048
1-4926
20O
0.982
!80
0.935
1.4891 240 -
~
230
1"170
1.5540
0.15
240
0-941 0.964
ks
35 -- 60
0.8 282-292 0-55
1!76-181
O.2
successfully [8]i Nitrolinoleum was made from collodion and " A N A Z " . :, tests showed that it completely fldfiUed the requirements of the GOST [St a~e Standard]. The nitrolinoleum based on " A N A z " was prepared b y the usual method and samples containing different a m o u n t s .of plasticizer were tested. The best results were obtained when 5 - 7 % of "ANAZ" was added to the collodion together with dibutyl phthalate. "ANAZ" m a y also be used successfully for the manufacture of plasticized rubber based on butadiene-nitryl rubber and "nairit" [9J; the results of the tests are given in Table 2 . . . . In the rubber based on butadiene-nitryl rubber a n d nairit, "ANAZ'," was tested in comparison with dibutyl phthalate and dibutyl sebaca~:*, High q u a l i t y paint-materials can be obtained from "ANAZ" plasticizer [10], for example nitro-enamel 507, in which it has successfully repla0ed castor oil. In their low degree of sweating, coatings made with "ANAZ" are superior to standar d coatings. "Perehlorovinyl" enamels made with the addition of "ANAZ" have also been investigated, in comparison with enamels prepared with tricresyl phosphate [1!]. The coating containing "ANAZ" are not inferior in their properties to the coatings with tricresyl phosphate, and have even better resistance to ageing. * The tests were carried out in ~heScientific Research Institute of the Rubber Industry (Moscow).
New plast~cizers f r m ~ k e r ~ , e naphthenie acids
507
TABLE 2.~RESULTSOF TESTSOF PLASTICIZEDRUBBER
]
Amount of plas-
t
4
tielzer, l~Iame of plasticizer
Relative Residue elonga- elonga tion, % tion, %
]byKar-
parts by weight per 100 parts of rubber
r rer's / method
•
Coefieient of frost resistanee at --25 ° I¸
•
SKN-26 Control mixture (without plasticizer) Dibutylphthalate
"ANAZ"
10 20 30
74 66 61 55
0-10 0.23 0.32 0.44
281 312 281 207
469 583 670 692
12 13 19 21
0.20 0-24 0.31 0-32
10 20 3O
64 58 53
0.25 0-35 0.42
283 256.5 218
551.5 646.7 689.5
12.1 14.0 15.0
0.33 0.41 0.51
154 128 133 113 126 119 11 L
488 566 616 620 718 626 646
8 11.2 14 14 13.6 8"8 11.2
0.21
"Nairit" Control mixture (without plasticizer) Dibutylphthalate "ANAZ"
m
10 20 30 I0 20 • 30 -
68 65 60 53 53 53 47
0.57 0.48 0.55 0.65 0.61 0.69 0.73
0.48 0-45 0.54
Samples o f d e r m a t i n [leatherette] in which t h e c a s t o r oil h a d been comp l e t e l y replaced b y " A N A Z " showed t h a t t h e latter, p r e p a r e d from n a p h t h e n i c acid fractions, is a high-quality plasticizer for this product. P r o d u c t s with different plasticizing properties c a n be o b t a i n e d according to t h e fractional composition o f the initial n a p h t h e n i c acids. T h e tests in the p r o d u c t i o n o f d e r m a t i n o f t h r e e samples o f this plasticizer synthesized f r o m t h r e e different fractions o f kerosine acidol were carried o u t o n the individual fractions o f " A N A Z " a n d on m i x t u r e s o f t h e m . T h e articles p r e p a r e d with " A N A Z " possessed good frost resistance. Table 3 gives t h e physicochemical characteristics o f the " A N A Z " fractions a n d t h e i r miscibility with various solvents. Because " A N A Z " is o n l y slight]y coloured it can be used to m a k e d e r m a t i n s o f pale shades, as has been confirmed b y trials. " A N A Z " as su¢h a n d in t h e f o r m o f films possesses a v e r y low volatility, good light-resistance, insolubility in water, stabilitY t o h e a t a n d cold, t h e
SHA~lrHALMAMBDOVe~ a/.
508
TABLE 3. PHYSICOCHEMICALCHARACTERISTICSOF "ANAZ" FRACTION8 Properties of the "ANAZ" fraction B. p., oc/3 nun H g
Solidification point, °C Acid number Saponification number Volatility a~ I~;0° Viscosity in the Ford-Engler apparatus at 20 °, see Viscosity according to Engler at 20 ° at 100 ° Miscibility: alcohol 1:1 gasoline 1:1 ethylacetate 1:1 castor oil 1:1 oxidized cotton seed oil water Odour Colour
Sample 1
Sample 2
Sample 3
190-240 -65
205-250 -58
0-994
0-998
0.34 291 "8 1.474 0.044
0.46 250.1 1.480 0-9
220-260 -40 1.002 0.42 249.6 1.481 0.068
Miffiture 3.5:3:1 190-260 -55 0.996
0"37 276.5 1"476
10
12
5.78
10.5 1-73
1"53
Miscible
60% separates out Miscible
Miscible
Immiscible Weak Pale yellow Light yellow I
absence o f t o x i c i t y , good c o m p a t i b i l i t y with film-forming agents a n d solvents, and a low solidification point, as can be clearly seen f r o m t h e Tables given. D e r m a t i n p r e p a r e d with " A N A Z " is n o t sticky a n d can be f o r m e d into rolls i m m e d i a t e l y a f t e r m a n u f a c t u r e . T h e samples o f d e r m a t i n m a d e were k e p t a t 70 ° for 8 h r in folded f o r m u n d e r a load o f 1 kg. T h e plasticizer did n o t s w e a t u n d e r these conditions.
EXPERIMENTAL 1200 g o f distilled naphthenic acids f r o m a kerosine fraction boiling within the r a n g e f r o m 115 to 140°/3ram H g a n d h a v i n g a n acid n u m b e r o f 295 was placed in a 3-1itre t h r e e - n e c k e d flask fitted with a mechanical stirrer, a reflux condenser with a w a t e r - s e p a r a t o r (of t h e D e a n a n d S t a r k t y p e ) , a d r o p p i n g funnel, a n d a t h e r m o m e t e r . T h e flask was h e a t e d t o 50 ° a n d 318 g o f p o w d e r e d caustic soda was a d d e d in portions o v e r 2 hr with continuous s~irring; its a d d i t i o n was c o m p l e t e d a t 100 °, a f t e r which, t o r e m o v e t h e w a t e r formed, the t e m p e r a t u r e o f the r e a c t i o n m i x t u r e was slowly raised. Elimination o f the w a t e r was completed a t 195-200 °. T h e t o t a l a m o u n t o f distillate
New plasticizers from kerosine naphthenic acids
509
obtained was ~140 ml. With the reaction mixture at 195-200 °, dichloroethane was added in drops from the dropping funnel. The dichlorocthane which had not reacted, on evaporating off, was condensed in the condenser and ran into the water-separator where it was separated from the water and drawn off through a cock. After sore9 time, when the evolution of water had ceased, the dichloroethane in the form of an azeetropie mixture running from the condenser was returned to the reaction flask. As the dichloroethane was added the reaction mixture became more mobile and sodium chloride separated. I n all, ~650 g of dichloroethane was added of which ~400 g reacted. The esterification process can be carried out in 6-8 hr. The reaction mixture was cooled to 50-60 °, 250-300 ml of water was added and the lower aqueous salt layer was separated from the upper layer. The upper layer was washed with water and after settling was distilled in a vacuum of 1 mm Hg. The yields of the fractions were as follows: I (100-185°) II (185-200°) III (200-240°) Residuo
-- 60 g; -- 170 g; --910 g; -- 50 g.
Fraction I I I consisted of the finished "ANAZ" plasticizer: yield 76o/0. For properties see Table 1. SUMMARY
1. A method for obtaining glycol esters of naphthenic acids has been developed and the applicability of this method for the production of glycol esters of other acids has been established. 2. The plasticizing and other properties of the plasticizer "ANAZ" [glycol esters of naphthenic acids] in rubber, nitrocellulose, perchlorinated vinyl resins, and polyvinyl and nitrocellulose compositions has been studied. The results of the trials have shown its excellent plasticizing properties and complete suitability for use. Translated by
B . J. H A Z Z A R D
REFERENCES
1. A. Ya. DRINBERG, Tekhnologiya plenkoobrazuyushchikh veshchestv. (Technology of Film-forming Substances.) Goskhimizdat, Leningrad and Moscow, p. 96, 1955 2. C. ELLIS, Khimiya uglevodorodov nefti i ikh proizvodnykh. (Chemistry of the Hydrocarbons of Petroleltrn and Their Derivatives.) United Scientific and Technical Pub]ishing House, Moscow, p. 562, 1938 3. C. Wt~RTZ, Ann. 116, 249, 1860; Ann. 113, 255, 1860 4. K. H. MEYER, German Pat. 332,677, 1919; Chem. Zbl. II, 646, 1921 5. A. ENGELHARDT, German Pat. 404,999, 1919; Chem Zbl. B 1, 1529, 1925
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SHAMKHALMAMEDOVet al.
6. E. E. AYRES and E. H. HAABESTAD, Canad. Pat. 286,077, 1929; Chem. Abstr. 28, 1417, 1929 7. SHAMIKHAL MAMEDOV, R. R. PASHAYEV, I. L. NIZKER and A. S. RZAYEV, U.S.S.R. Authors' Certificate ] 14,337, 1958 8. SHAMKHAL MAMEDOV, A. S. RZAYEV and I. L. NIZKER, Khim. prom. ~o. 7, 26, 1960 9. SHAMKHAL MAMEDOV, A. S. NOVIKOV. G. V. DOROKHINA, A. S. RZAYEV and I. L. NIZKER, U.S.S.R. Authors' Certificate 132,803, 1960 10. SHAMKHAL MAMEDOV, A. S. RZAYEV and I. L. NIZKER, U.S.S.R. Authors' Certificate 124,573, 1959 11. SHAMKHAL MAMEDOV, I. L. NIZKER and A. S. RZAYEV, U.S.S.R. Authors' Certificate 124,574, 1959