EPOX I D E PLAST I CIZ E R-STA B I LI Z ER FO R POLY(VINYL CHLORIDE) FROM a-CAMPHOLENOL, A TERPENE-DERIVED PRIMARY ALCOHOL .
. F. C.
J
B
LEW IS
,
.Vaial Stores Laboratory: Olustee, Fla.
M A G N E , Southern C!ilization Resenrch 2 Derelopment Dizision. Agricidtural Research Serzice, C: S. Department of Agriculture: .\-el0 Orleans. La.
G
.W .
H E D R I C K , .Vacal Stores Laboratorj. Olustee, Fla.
The alcohol a-campholenol (2,2,3-trimethyl-3-cyclopentene- 1 -ethanol) was esterified with acids such as decanoic acid, commercial fatty acids, o-phthalic acid, oleic acid, and a-campholenic acid. Epoxidized esters of the alkanoic and alkenoic acids were acceptable primary plasticizers for poly(viny1 chloride) with excellent long-term thermal stability.
N I N V E S T I G A T I O ~ S to increase utilization of turpentine, re-
I search on
a-campholenealdehyde (11) was undertaken. Following the procedure of Arbusow ( 7 ) on a fairly large laboratory scale, 857, yields of (11) were obtained by zinc bromide-catalyzed rearrangement of a-pinene epoxide (I). if the catalyst was prepared properly. T h e preparation of 11, its conversion to a-campholenol (2.2,3-trimethyl-3-cyclopentene-1-ethanol) (111). and study of the epoxide (I\.) of acampholenyl acetate (V) are reported elsewhere ( 4 ) . The purpose of this report is to describe synthesis and some properties of esters of a-campholenol (111), conversion of the esters to epoxides, and evaluation of the epoxides as plasticizerstabilizers for poly(viny1 chloride) polymers. The esters investigated were made from o-phthalic acid, oleic acid. decanoic acid, a-campholenic acid (2,2.3-trimethyl-3-cyclopentene-lacetic acid) (VI) (61, and a fatty acid from animal fat. Experimental
Preparation and characterization of a-campholenol (111) and the a-campholenic ester are discussed bv Lelvis and Hedrick ( 4 ) . Except for the a-campholenic ester, the esters irere prepared by reaction of the acid and a-campholenol in benzene or toluene usingp- toluenesulfonic acid as a catalyst. 12'ater from the reaction was removed by azeotropic distillation. Since rearrangement of the alcohol to P-campholenol (2.3.3-tri-
methyl-1-cyclopentene-1-ethanol) (LYI) \vas a possibility (I). a sample of the decanoic acid ester \vas saponified. The recovered alcohol \vas not altered during processing. A typical epoxide preparation is cove;ed in the follo\ving description of the epoxidation of a-campholenyl oleate. CYCampholenyl oleate (94 grams. 0.224 mole) \vas disso!ved in 520 ml. of diethyl ether and epoxidized by s l o ~ vaddition (2 hours) of 101 grams, 10% excess. 85% m-chloroperbenzoic acid (MCPB). dissolved in 500 ml. of diethyl ether a t 15' to 20' C. After agitation for an additional 2 hours. the batch \vas stored in a refrigerator overnight a t 5 '. .Analysis of a sample for excess XlCPB indicated that the reaction \vas complete. By--product m-chlorobenzoic acid and excess MCPB \yere removed by ivashing \\.ith dilute alkali and \cater. A negative test for peracid \vas obtained on the ether. solution when analyzed by the method described in a technical data sheet (2). The usual caution was observed in removing peracids before continuing \vith the isolation of the epoxide. The solution was dried over sodium sulfate and stripped of ether first \vith a \vater aspirator and finally \vith a mechanical pump a t 1.0-mm. pressure-95 grams of colorless liquid. 957, yield. T h e epoxides were not distilled. Properties of esters and epoxides are tabulated in Tables I and 11. The folloiving formulation \vas employed in evaluating the esters of Table I1 as plasticizers for a poly(viny1 chloride-vinyl acetate) 95 : 5 copolymer.
5 Resin (Vinylite VYN\V-5) Plasticizer Stearic acid Stabilizer (basic lead carbonate)
0.5 1. o
Table 1. Yield, Ester Oleatea Decanoate a-Campholenate Phthalate, crude
yc
Esters of a-Campholenol Hydrogenation Equivalent Formula M o l . W7t. Calcd. Found G 8 H j o O 2 418.68 209.34 204.1 C ~ O H ~ ~ O 308.49 L' 308.49 306,O CnoH820~ 304.46 CzsHasOd 438.58
63.5 35.0
Sapontfication Equicalent Calcd. Found 418.68 416.1 308.49 306.0 304.46 308.9
B.P.'. /.Urn. n',"" 186/0,05 1 ,4707 136j0.1 1 ,4614 172/3.0 1.4821 Decomp. 190/0.1 190/0.1 431 , 2 2 Fatty acidc 66 a Oleic acid, neutralization equiralent calcd. for ClsHaAO? 282.46. Found 275.5. Hydrogenation equicalent found 268.34. Stripped at 770a, 0.1 mm. Commercial animal acid; neutral equiralent found. 295, $85 oleic acid. Distilled bulb-io-bulb, sample x a s crude and analjtical data w r e not taken on this nor phthalate ester. 90.0 89.6 66 100b
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Epoxides of Esters of a-Campholenol Oxirane Oxygen ( 3 ) ,yc Ester Calcd. Found Oleate 7.64 6,69 Decanoate 5.12 4.55 a-Campholenate 10.55 8.66 Phthalate, crude Fatty acida 8.5 5 26 9 5.93 5.63 Commercial animal acid, neutral equivalent found 295, 487, oleic acid. Table II.
a
CH2CH0
n
I
-+&
-
CH2CH20H
P
+
O
b
0 CH2CH20CCH3
PT
60 W 0
z a c
0
w
-I LL W
40
a
PII
20
0
0.5 I. 0 1.5 HOURS EXPOSURE AT 176 *C
2.0
Figure 1. Thermal stabilities of a-campholenyl epoxide ester-copolymer compositions 1. 2. 3.
4. 5. 6.
a-Campholenyl decanaate epoxide Di-a-campholenyl phthalate diepaxide a-Campholenyl epoxide ester of animal a-Comphalenyl campholenate diepoxide a-Camphaienyl oleate diepoxide Control (DOP)
acids
Table 111.
Comfiosition 1 2 3 4 5 6 a
232
These formulations, with the exception of the one incorporating a-campholenyl phthalate diepoxide, were readily milled and molded a t 310' F. The latter formulation required a higher temperature (330' F.) for satisfactory processing. Tensile strength, 100% modulus, elongation, and brittle point were determined as previously reported (5) on test specimens die-cut frcm a 75-mil molded slab. Extraction loss after steeping for 24 hours a t 60' C. in a 1% Ivory soap solution and volatility loss (ASTM 1203-61T) were determined on 10- to 20-mil sheets. Relative thermal stabilities are reported in terms of the amber O", 45' directional reflectance as measured by a Photovolt Reflectometer No. 610 on test panels of the milled sheets after exposure to 176' C. for various periods of time. Compositions Ivere rated compatible if no exudation or spew developed during 150 days' shelf storage a t room temperature. The results of these tests for the various epoxide ester-resin compositions, as well as that for the control, di-2-ethylhexyl phthalate-resin composition, are reported in Table I11 and Figure 1. These are all compatible.
Physical Characteristics of a-Campholenyl Epoxide Ester-Vinyl Copolymer (VYNW-5) Compositions Tensile 100% Brittle Strength, Modulus, Elongation, Point, Volatility Extraction CornpatiP.S.I. P .s.I. 70 70 Loss, Loss, 70 bility Plasticizer 3570 of or-Campholenyl decanoate 2980 1350 380 - 37 7.6 18.7 C epoxide a-Campholenyl phthalate 9500 G 4 $40 0.1 0.4 C diepoxide a-Campholenyl ester of 2920 1700 360 - 29 0.6 0.6 C epoxided animal acids Q C a-Campholenyl campholenate 3890 45 f22 1.6 ... diepoxide a-Campholenyl oleate 3050 1500 380 - 23 0.5 12.3 C diepoxide DOP (Control) 3050 1610 330 - 33 1.50 1. o
Samples broke before elongating 103%.
I & E C PRODUCT RESEARCH A N D DEVELOPMENT
The results clearly show that the campholenyl epoxide esters of the fatty acids employed in compositions 1, 3, and 5 are the best performing plasticizers of the group in terms of ease of processing, low-temperature performance, and flexibility imparted to the plastic compositions. I n these respects they are about comparable to the control (composition 6) but impart thermal stabilization to the plastic composition (curves 1, 3: and 5 of Figure 1) vastly superior to that of D O P (curve 6 ) . There is no explanation a t this time for the discrepancy in the values for extraction loss of compositions 3 and 5. The animal fatty acid contained 48Yc oleic acid. A loss in the order of 6Yc, approximately one-half that obtained for composition 5, Lsould be expected for the ester made from this acid. The campholenyl epoxide esters of the carbocyclic acids (compositions 2 and 4) are decidedly more poorly performing plasticizers and stabilizers (curves 2 and 4, Figure 1). In fact? the composition plasticized isith di-a-campholenyl phthalate diepoxide (curve 2> Figure 1) exhibits an even poorer thermal stability than that of D O P (curve 6 ) . The poor stabilization imparted by the cyclic acid epoxide esters is surprising in vie\s of their oxirane Content: which is equal to or greater than that of the noncyclic acid esters and must be indicative of either a loss in oxirane content during processing or a loiser reactivity of the oxirane group.
Conclusions
a-Campholenol (111) can be esterified with fatty acids. I11 was not rearranged to P-campholenol (VII) in preparation of the ester. T h e a-campholenyl epoxy esters of noncyclic alkanoic or alkenoic acids are acceptable primary plasticizers for poly(viny1 chloride), Lvhich impart middle-range lowtemperature performance and excellent long-term thermal stability to the plastic composition. Carbocyclic esters of acampholenyl epoxide, though compatible, are far less effective plasticizers and stabilizers and contribute little to low-temperature performance. literature Cited (1) Xrbusow. B., Ber. 68, 1430 (1935). ( 2 ) Food Machinery Gorp.. Inorganic Division, Product Promotion Department. 633 Third Xve.. New York. N. Y . . Technical Data Sh’eet. m-Chloroperbenzoic Acid. 162. (3) Jungnickel. J. L..Peters. E. D.. Polgar. A . \Veiss. F. T.,
“Organic .Analysis.” Vol. I, p. 135, Interscience. New York, 1953. (4) Lewis, J . B.: Hedrick, G. \V,, J . Orp. Chem.. in press. (5) Magne. F. C., Mod, R. R., J . Am. Oil Chemists’ Soc. 30, 269-271 (1933). (6) Tieniann, F.:Ber. 29, 3007 (1896). RECEIVEDfor reviev June 18, 1965 .ACCEPTED September 30. 1965
ADSORPTION AND DESORPTION OF A SURFACE ACTIVE AMINOAMIDE ON AN OXIDIZED IRON SURFACE G. J .
K A U T S K Y AND
M . R .
BARUSCH
Charon Research Go.: Richmond, Caiq.
A study o f the adsorption of a C1*-labeled aminoamide of oleic acid from dilute hydrocarbon solutions on iron filings showed that a thin film of the aminoamide was adsorbed on the surface. The object of the study was to measure desorption of the surfactant into hydrocarbons and to determine if the desorption could b e enhanced b y polar compounds. About 2070 of the adsorbed aminoamide desorbed relatively rapidly into hydrocarbons; the remainder desorbed much more slowly. Polar compounds in hydrocarbon solution promoted desorption of the surfactant. This principle was useful in the operation of product pipelines. Purging a surfactant from the pipeline walls with 2-propanol protected subsequent shipments of petroleum products from contamination and prevented degradation of water reaction properties of aircraft fuels.
and desorption of a surface active aminoamide were investigated in connection Lvirh a field problem encountered in petroleum product pipelines. hfilitary aircraft fuels. after being transported through a product pipeline. occasionallv fail \\ ater reaction tests. This degradation of water reaction properties \\as believed to be due to desorption of surfactants \I hich had been adsorbed on the Ivalls of the pipe during previous shipments of motor gasoline. Motor gasolines often contain small amounts of additives such as corrosion inhibitors, detergents, and carburetor deicing agents, which have a strong tendency to adsorb on metal sur-
A
DSORPTION
faces. .4mong the most effective types of surfactants are the aminoamides 1% hich result from the reaction of aminoethylor hydroxyerhyl-substitutedethylenediamine with a carboxylic acid such as oleic acid or stearic acid (7. 3, 6). The polyfunctionality of such aminoamides promotes stronger adsorption on metal surfaces relative to simple primary or secondary amines (2). IVhen a gasoline containing a surfactant is transported through a pipeline. some of the surfactant is adsorbed on the internal wall of the pipe. The adsorbed film of surfactant can desorb into subsequent shipments of products. Desorption of surfactants into aircraft fuels is particularly VOL. 4
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