The catalyst recycle studies were conducted using the Rh(P@3)2(CO)C1-excesstriphenylphosphine catalyst system dissolved in a high boiling solvent, dioctyl phthalate (b.p. ca. 380” a t 1 atm.). The olefin feedstock consisted of a commercial blend of alpha-olefins in the C- to Clo range. Two batch reactions were performed using fresh catalyst solution and a recycle catalyst solution remaining after distillation of product from the first batch run. A GC analysis of the catalyst solution after distillation showed very little aldehyde left, that remaining being mainly the n-C,, aldehyde, which is the highest boiling product. The recycle catalyst solution was diluted with fresh solvent and then used for hydroformylation of a second portion of the olefin blend. Both reaction rate and the visual appearance of the catalyst solution (a bright yellow color) indicated that no deterioration of the catalyst had occurred in handling or distillation. Finally, GC analysis of the reaction product demonstrated that no adverse effects upon product selectivity and isomer distribution had occurred. The results of GC analysis and reaction conditions for the distillation are summarized in Table VII.
Bird, C. W., ‘(Transition Metal Intermediates in Organic Synthesis,” Chap. 6, Logos Press, London, 1967. Chatt, J., Shaw, B. L., J . Chem. Soc. 1966A, 1437. Evans, D., Osborn, J. A., Wilkinson, G., J . Chem. Soc. 1968A, 3133. Hagemeyer, H . J. (to Eastman Kodak Co.), U.S. Patent 2,576,113 (Nov: 27, 1951). Hagemeyer, H. J., Hull, D. C. (to Eastman Kodak Co.), U.S. Patent 2,694,734 (Nov. 16, 1954). Jardine, F. H., Osborn, J. A., Wilkinson, G., Young, J. R., Chem. Ind. 1965, 560. Osborn, J. A., Jardine, F. H., Young, J. F., Wilkinson, G., J . Chem. Soc. 1966A, 1711. Osborn, J. A., Wilkinson, G., Young, J. R., Chem. Comm. 1965, 17. Pruett, R. L., Smith, J. A., Abstracts, 154th ACS Meeting, Sept. 10-15, 1967, Chicago, N-39. Pruett, R. L., Smith, J. A., J . Org. Chem. 34, 327 (1969). Slaugh, L. H., Mullineaux, R. D., J . Organometal. Chem. 13, 469 (1968); U. S. Patent 3,239,566 (1966a), 3,239,569 (1966b), 3,239,570 ( 1 9 6 6 ~ )C; A 59, 1 1 2 6 8 ~(1963). Wender, K., Sternberg, H. W., Orchin, M., in “Catalysis,” P. H. Emmett, Ed., Vol. 5 , Chap. 2, Reinhold, New York. 1957.
Acknowledgment
The authors express appreciation to K. K. Robinson for assistance with experimental work. RECEIVED for review December 30, 1968 ACCEPTED June 1, 1969
literature Cited
Benzoni, L., Andreeta, A., Zanzottera, C., Camia, M., Chem. Id.(Milan) 48, 1076 (1966).
Presented a t First North American Meeting of Catalysis Society, Atlantic City, KJ.,February 20, 1969.
NAVAL STORES PRODUCTS FROM PONDEROSA PINE STUMPS T. P R O V E A U X , A N D R A Y V . L A W R E N C E Naval Stores Laboratory, Southern Utilization Research and Development Diuision, Agricultural Research Service, U . S . Department of Agriculture, Olustee, Fla. 32072
N.
M A S O N
R O L A N D
1.
J O Y E ,
J R . ,
A .
BARGER
Rocky Mountain Forest and Experimental Station, Flagstaff, A r k . 86001 Extractives from ponderosa pine ( Pinus ponderosa Laws) stumps were processed and the rosin, pine oil, and turpentine recovered. Comparison with equivalent connmercial products indicates that further processing would be required before these products could be substituted in most commercial uses.
WOOD rosin, turpentine, and pine oil are produced com-
Method of Sampling
mercially from extractives from southern pine stumps. Other areas of this country have pines and pine stumps that could be utilized by the naval stores industry. Anderson (1947,1954,1955,1962) and Riffer and Anderson (1966) have studied the composition of extracts of ponderosa stumps from recently felled trees as well as new and old stumps. I n this study, rosin was prepared from the extracts, and its physical and chemical constants were determined. I n so far as could be determined, this was the first study on the composition of ponderosa pine oil and rosin.
Stumps from several areas were selected to represent sound ponderosa pine stumps from trees logged between 1909 and 1925. They were sound, with no internal or root rot but without sapwood left. Although stumps were selected to represent average conditions, a much larger selection would be required to give a completely accurate analysis of stump quality. Also, the small samples used in this work probably contained less trash, decayed wood, and other undesirable material than would be present in the wood used in a large scale operation. While the VOL. 8 NO. 3 S E P T E M B E R 1969
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yield of extractable material obtained in this test agrees well with that previously reported (Anderson, 1947, 1962; Riffer and Anderson, 1966), it is probably higher than could be maintained in a commercial operation. Stumps were pulled and cut with a chain saw a t 1- to 4-inch intervals down the stumps. The chips were sealed in plastic bags and sent to the laboratory for extraction. Fifteen ponderosa pine stumps from five different areas were examined. Three stumps were selected from each of four different areas and three of these stumps were divided into top, intermediate, and root sections for analysis.
points. The yield of hexane extract ranged from 21 to 31%, an average of 27%. The benzene extract following the hexane extraction gave a dark rosin with a high softening point. The total yield of extract (hexane and benzene) was slightly higher than when benzene alone was used. The major difference between the products from ponderosa pine stump extracts and those from southern pine stump extracts was the presence of relatively large amounts of longifolene in the pine oil fraction and A3-carene in the turpentine fraction. Longifolene is a sesquiterpene and is not present in pine oils from southern pine stumps. The pine oil less the longifolene is very similar to commercial pine oils. I t contains about 60% a-terpineol, 8% borneol, 7% a-fenchyl alcohol and terpin-1-01, 6% each terpin4-01 and dihydro-a-terpineol, 5% cis-anethole, and smaller amounts of camphor, isoborneol, trans-anethole, and hydroxy-p-cymene. The volatile terpenes or turpentine fraction was found to contain 42% a-pinene and 43% A3-carene. Terpenes present in small amounts include camphene, 8-pinene, a-terpinene, limonene, and p-cymene. Turpentine from southern pine stumps contains little or no A3-carene and usually has a moderate amount of terpinolene which is not present in the ponderosa pine stump turpentine. Ponderosa wood rosin contains about 75 to 85% resin acids, the same as in commercial wood rosins and in about the same amounts. The rosin has a lower acid number than commercial wood rosin, which is due to unidentified neutral materials. On vacuum distillation, most of these neutral materials can be removed in the first fraction and account for 10 to 15% of the weight of the rosin. Table I1 summarizes the data on the composition of the turpentine, pine oil, and rosin.
Extraction and Analysis
In the laboratory, 600 grams of chips were weighed in duplicate into 5-liter three-necked flasks. Each sample was stirred and extracted with refluxing benzene for 2 hours. The hot benzene extract was filtered and the extraction repeated with fresh benzene. The two extracts were combined, the benzene removed by distillation, and the residue steam-sparged to a temperature of 165-70" C. and a turpentine-water ratio of less than 1 to 20. The pine oil was distilled from the residue a t 165-70°C., under vacuum (0.2 to 0.3 mm. of Hg). The resulting product was poured into aluminum cups and color grade and softening point molds. The amount of benzene-soluble extract obtained from the various stump samples and the composition of the extract are reported in Table I. The yield of extract ranged from 26 to 34%, an average of 31%. This corresponds to approximately 600 pounds of extract per ton of stump wood. Stump chips were also extracted first with hexane and then with benzene and the two extracts processed separately. The hexane extracts gave lighter colored rosins with lower softening
Table I. Hexane and Benzene Extractives in Ponderosa Pine Stumps Composition of Extractiws Extract No.
Extract
Turpentine
Pine oil
2 3 4 5 6 7 8 9 10 11 12 Av.
21 25 22 35 28 29 21 23 29 28 30 31 27
9.2 7.2 9.8 9.3 9.0 8.9 8.9 8.8 8.0 7.2 8.4 10.8 8.8
7.4 5.1 7.1 5.8 6.9 5.1 6.1 5.9 5.7 5.5 6.1 7.0 6.1
13 14 15 16 17 18 19 20 Av.
29 34 29 26 33 32 30 34 31
10.1 9.6 11.7 9.1 9.0 7.0 11.4 10.8 9.6
6.5 6.6 9.4 6.2 6.4 6.4 8.5 5.3 6.9
C' /o
Longifolene"
Rosin Properties Rosin
Color grade
A.N.'
S.P., C.'
H I G H H G H G G H H H
149 147 149 154 153 155 147 149 159 146 147 147
68-69 64-65 66-67 71-73 70 74-75 56-57 61-62 70-71 66-68 67-68 67-69
D D D D
140 147 155 143 147 145 140 148
68-70 69-70 77-79 73-74 70-71 78-79 69 78
HEXANEEXTRACTS 1
6.4 4.7 5.7 4.6 5.8 4.6 5.7 4.9 5.2 5.1 5.0 6.5 5.3
77 83 77 78 80 78 79 81 81 82 81 76 79
BENZENE EXTRACTS 5.6 4.7 8.8 7.2 5.6 3.9 7.7 5.7 6.2
78 79 70 77 79 78 71 78 76
E D E D
Turpentine, pine oil, and longifoleze fractions analyzed by gas chromatography, percentages of each fraction corrected when contaminated with one of other fractions. 'Acid number determined by titration with alkali. 'Softening point, A S T M ball and ring procedure.
298
I & E C PRODUCT RESEARCH A N D DEVELOPMENT
Table II. Average Composition of Turpentine, Pine Oil, and Rosin from Ponderosa Pine Stumps
Turpentine Composition, cic a-Pinene Camphene &Pinene a3-Carene
42 1.0 4.7 43
1.4 5.7 2.2
a-Terpinene Limonene Unidentified peaks
I ' m Oil Composition, R Camphor Dihydro-aterpineol a-Fenchyl alcohol and terpin-1-01 Terpin-4-01 @-Terpineol
3.8 6.2 7.0 6.3 1.3
2.5 57 8.2
Isoborneol a-Terpineol Borneol Anethole cis trans
2.6 5.1
Rosin Acid Composition, % Pimaric Sandaraco-pimaric Palustric Isopimaric
9.9 4.5 9.9 9.1
Dehydroabietic Abietic Neoabietic Unidentified acids
23.2 30.5 4.5 7.3
69°C.) in 71% yield. The rosin recovered by stripping the column with alcohol was dark in color, had a low acid number (129) and a high softening point (76-77" C.), and amounted to 29% of the original rosin. Another method for removing the color bodies and oxidized constituents of wood rosin, by the selective solvent action of furfural (Humphrey, 1943), was applied to the ponderosa pine stump rosin, and a lighter colored rosin (N color grade) with an acid number of 165 and softening point of 67-68°C. was recovered in 75% yield. The recovered rosin containing the color bodies and oxidized constituents had a low acid number (130) and a high softening point (76-78" C.). Both methods gave a pale wood rosin that resembled commercial wood rosins. Unlike Anderson (1947, 1955, 1962), we found no evidence of fatty acids in either the extract or the wood rosin. I t appears that the more seasoned sound ponderosa pine stumps also give higher yields of extractives than the younger stump extractives described by Anderson (1947). The yield of total extractives exceeds that from southern pine stumps. Conclusions
The resin acid composition was determined by gas chromatography, using the method described by Joye and Lawrence (1967). The turpentine and pine oil analyses were run on a 15-foot x %e-inch 5% Carbowax 20M column and the peaks identified by comparison of retention times with known terpenes. The terpene peaks were collected and their infrared spectra obtained and compared with authentic samples for identification. Most of the pine oil components were collected off the gas chromatograph and compared directly with authentic samples for identification. Table I gives some of the physical characteristics of the wood rosins obtained from ponderosa pine stumps. The lower acid number is the major difference between ponderosa pine stump rosin and commercial wood rosins. Two methods currently used to refine wood rosin were applied to the ponderosa pine stump rosin. The method described by Palmer (1934) using a n absorbent such as fuller's earth to remove the color bodies or oxidized constituents gave a light colored rosin (color grade X+) with an improved acid number (167) and softening point (68-
Ponderosa pine stumps could be utilized as a source of naval stores products, which, while different from equivalent commercial products, might find similar applications. More compositional knowledge and process development are needed to determine how to make the ponderosa pine stump products suitable for uses currently met by southeastern pine stump products. literature Cited
Anderson, A. B., Forest Prod. J . 12, 417 (1955). Anderson, A. B., Ind. Eng. Chem. 39, 1664 (1947). Anderson, A. B., J. Inst. Wood Sci. 10,29 (1962). Anderson, A. B., T A P P I 37,7,316 (1954). Humphrey, I. W., Ind. Eng. Chem. 35, 1063 (1943). Joye, N. M., Lawrence, R. V., J . Chem. Eng. Data 12, 279 (1967). Palmer, R. C., Ind. Eng. Chem. 26, 703 (1934). Riffer, R., Anderson, A. B., Holzforschung. 20, 1, 37 (1966). RECEIVED for review January 10, 1969 ACCEPTED May 14, 1969
ET H Y LE NE- PRIOPY LE NE C0POLYMER F L U I D A Stable High- Viscosity-Index Base Oil D .
S .
GATES,
I .
N. DULING,
AND
Research & Development, Sun Oil Co., Marcus Hook, P a .
PREVIOUS papers have shown a close relationship between glass transition temperature and rate of change of viscosity with temperature for many fluids (Duling et al., 1966; Stearns et al., 1966). As the glass transition temperature of a fluid decreases, the change of viscosity with temperature decreases-i.e., the viscosity index (VI) increases. Maurer (1965) has shown that the glass transition temperature (Tg) for randiom ethylene-propylene copolymers decreases regularly with increasing ethylene content. Also,
R .
5 .
STEARNS
19061
the degree of crystallinity and the melting point approach a minimum and disappear in the intermediate copolymer compositions. As the ethylene content increases, the size and number of the ethylene blocks increase and hence the crystallinity and melting point increase. Similarly, as the propylene content increases, the formation of crystallizable propylene sequences increases. Perhaps ethylene-propylene copolymer fluids of the proper composition would possess low Tg's, excellent viscosity temperature VOL. 8 N O . 3 S E P T E M B E R 1969
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