DOCSLIB.ORG

By 92.--Stoute ATTORNEYS Aug

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
By 92.--Stoute ATTORNEYS Aug Aug. 6, 1968 C. B. MCCARTY EAL 3,396,204 HYDROBROMINATION OF OLEFINS IN A THIN TURBULENT FILM Filed Feb. 4, 1965 2 Sheets-Sheet 29 OLE FIN RAW MATERAL H4 HYDROGEN BROMIDE 34 INVENTORS Kenneth W. Theie Chorles B. McCorty By 92.--Stoute ATTORNEYS Aug. 6, 1968 C. B. MCCARTY ETAL 3,396,204 HYDROBROMINATION OF OLEFINS IN A THIN TURBULENT FILM Filed Feb. 4, 1965 2 Sheets-Sheet 2 COOLANT NLET OLEFN NLET HYDROGEN BROMIDE NLET Fig. 2 INVENTORS Kenneth W. The ille Chorles B. McCorty BY W. C.Cutba. 42 2 4 a ATTORNEYs — 3,396,204 3 4. a supply of cooling liquid 19, and inlet line 36, and an can be used in conjunction with an inert carrying gas or exit line 21. The reaction mixture exits rapidly from the driving gas stream such as nitrogen and the like. In a end of the reaction tube 13, into a separator 26, contain preferred embodiment, however, the hydrogen bromide is ing a mist eliminator 27. The reaction product is re brought into contact with the olefin reactant with such covered via a recovery line 28, leading from separator velocity that it is capable of being the sole propelling force 26. Unreacted hydrogen bromide is also recovered and for forming and maintaining a film of the olefin reactant. recycled through line 29, to the initial hydrogen bromide Inert ingredients when present in the hydrogen bromide feed line 5. driving gas are not necessarily harmful, but in the interest The description of the invention above in terms of a of economy and simplicity of operation, it is preferable rising film reactor which is in communication with the to operate solely with hydrogen bromide gas. One con liquid alpha olefin and an inlet means for introducing a IO sideration here is that hydrogen bromide gas which has hydrogen bromide gas stream is not intended as a limita been prepared according to a well-known bromine burn tion on the proper scope of the present invention. Those ing process, also contains small amounts of hydrogen and skilled in the art will readily be able to envision modifica inert gases. Continuous use of this means as a source of tions to FIGURE 1, including concurrent and counter hydrogen bromide can result in the build-up of the hydro current falling films, horizontally propelled films, coil gen and inert gases within the system to the point where reactors, as well as others. It is intended that the proper they may interfere with the efficient operation. In that breadth to be attributed to the present invention should event, it may become necessary to either remove these cover any process which calls for contact between the materials from the system or else use the accumulated gaseous hydrogen bromide and a thin turbulent film of the 20 mixture of hydrogen bromide, hydrogen and inert gases alpha-olefin reactant. However, the rising film process, as as a separate hydrobrominating agent in an auxiliary or illustrated in more detail in the examples below, rep secondary hydrobrominating unit. It is possible, according resents the preferred embodiment of this invention, since to this invention to use one or more secondary hydro it affords very high quality reaction product in a rapid and brominating units in conjunction with the main reaction efficiently controlled process. Moreover, by the rising 25 system described herein. film process herein described it is possible to react hydro The velocity or rate of the hydrogen bromide gas neces gen bromide and alpha olefins at higher temperatures than sary to establish the turbulent film can be determined heretofore thought possible and still obtain excellent for any desired set of reaction conditions and procedures. results. The requirement varies for different apparatuses. Olefins which can be treated in accordance with the 30 It has been discovered that for the preferred rising present invention are normally liquid alpha-olefin hydro film reaction system described herein, the input rate of carbons containing from about 5 to about 30 carbon the hydrogen bromide raw material to the system should atoms, and preferably 10 to 20 carbon atoms. The olefins be in the range of from about 20 pounds per hour to can be obtained from any source and include products 'about 110 pounds per hour, and preferably between 25 of catalytic and thermal cracking of oils, and those ob to 85 pounds per hour. In addition to the initial hydrogen tained by dehydrogenating the corresponding paraffinic bromide feed inlet that introduces fresh hydrogen bromide hydrocarbon or by dehydrating alcohols. So-called ethyl to the system at the proportions specified above, there is ene build up alpha olefins can also be used. These com a Substantial amount of unreacted hydrogen bromide pounds are typically made by passing ethylene into a that is recycled within the system. This was pointed out trialkyl aluminum at about 200 F. to about 400 F. and 40 above in the discussion of FIGURE 1. The quantity which at atmospheric or higher pressure for a period of from is recycled is on the order of from about 5 to 40 cubic about several minutes to an hour or more. Alpha olefins feet per minute, and preferably from about 10 to about of various and predetermined chain lengths are thus ob 35 cubic feet per minute. This recycle stream of hydro tained but those containing from about 10 to about 20 gen bromide insures that the olefinic reaction mixture is carbon atoms are preferred for use in this invention. The 45 maintained in a turbulent annular film. It is sometimes raw material alpha olefins can be maintained at room desirable to circulate the recycled fraction to a com temperature and need no preheating or precooling steps pressor before passing it to the initial raw material feed before being brought into contact with the hydrogen line. bromide. Examples of suitable alpha olefins are decene, If desired, the recycling line may be omitted complete dodecene, tetradecene, hexadecene, octadecene, and eico 50 ly from the practice of the present invention. When this Sene. Usually these compounds are prepared as mixtures is done, however, the rate of the fresh supply of hydrogen by the processes mentioned above. Such mixtures can be bromide to the system must in any event be sufficient to used directly in this process. Pure olefins also find perfect establish and maintain the turbannular film flow. application according to the present invention. A horizontal or a slightly inclined reaction vessel may So far as the gaseous hydrogen bromide reactant is require an adjustment in the velocity of the hydrogen concerned, there are no special limitations such as source, bromide as compared for example to a vertical unit. A temperature, etc. The hydrogen bromide, for example, rising film process as described above and which repre can be prepared when and where needed, e.g. via a well Sents a preferred embodiment of the present process re known bromine burning process, and used directly. Any quires possibly the greatest velocity since it propels, car convenient source can be used. As with the olefin reactant, 60 ries and maintains the olefin up through the reaction zone no special precautions are necessary such as cooling or as an annular film. In a modification wherein a falling heating. It can be kept at room temperature and used in film of olefin is used instead of a rising film, the velocity that condition. requirement will be determined in part by whether the In the preferred embodiment of the present invention, gaseous hydrogen bromide is passed concurrently or the gaseous hydrogen bromide should be added to the 65 Countercurrently. Best reaction results are obtained when System at a 5 molar percent to 20 molar percent over the the olefin film is in a turbulent state and this fact can be stoichiometric amount, the excess being necessary be used as a guide in favoring any given velocity rate for the cause of the solubility of the hydrogen bromide in the gaSeous reactant. alkyl bromide reaction product. FIGURE 1 depicts the hydrogen bromide inlet tube As has been mentioned previously, the present process 70 35, as being disposed centrally within the vertical reaction does not require the presence of any ingredients other chamber 13. Variations on this apparatus structure can than hydrogen bromide, alpha olefins, and a free radical be employed without departing from the spirit of the initiator as described hereinafter. Materials including Sol present invention. Vents, driving or inert carrying gases, while not neces A Suitable rate of addition of the organic olefin re Sary, can be used. For example, the hydrogen bromide 75 actant can be fairly easily determined. It will be de 3,396,204 5 6 pendent to some extent, of course, on the velocity of the formation that is necessary to catalyze the free radical ad hydrogen bromide addition rate. So far as the rising film dition should be used. Accordingly, it has been found process is concerned, the rate of olefin addition can vary that about 0.005 mole percent to about 5.0 mole per between about 25 pounds per hour to about 200 pounds cent of ozone when added to the olefin gives consistently per hour. A preferred rate of addition found especially good results in the practice of the present invention. It suitable for rising film reactions described herein is from is preferred to use from about 0.01 mole percent to about about 50 to about 150 pounds per hour. 0.6 mole percent of ozone. It is to be appreciated that the The present process is not encumbered by any critical olefin converted to ozonide is essentially lost to the de requirements for conducting the novel process under sired alkyl monobromide reaction product emphasizing pressure.
Load more

Recommended publications
  • Catalytic Pyrolysis of Plastic Wastes for the Production of Liquid Fuels for Engines
    Electronic Supplementary Material (ESI) for RSC Advances. This journal is © The Royal Society of Chemistry 2019 Supporting information for: Catalytic pyrolysis of plastic wastes for the production of liquid fuels for engines Supattra Budsaereechaia, Andrew J. Huntb and Yuvarat Ngernyen*a aDepartment of Chemical Engineering, Faculty of Engineering, Khon Kaen University, Khon Kaen, 40002, Thailand. E-mail:[email protected] bMaterials Chemistry Research Center, Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen, 40002, Thailand Fig. S1 The process for pelletization of catalyst PS PS+bentonite PP ) t e PP+bentonite s f f o % ( LDPE e c n a t t LDPE+bentonite s i m s n HDPE a r T HDPE+bentonite Gasohol 91 Diesel 4000 3500 3000 2500 2000 1500 1000 500 Wavenumber (cm-1) Fig. S2 FTIR spectra of oil from pyrolysis of plastic waste type. Table S1 Compounds in oils (%Area) from the pyrolysis of plastic wastes as detected by GCMS analysis PS PP LDPE HDPE Gasohol 91 Diesel Compound NC C Compound NC C Compound NC C Compound NC C 1- 0 0.15 Pentane 1.13 1.29 n-Hexane 0.71 0.73 n-Hexane 0.65 0.64 Butane, 2- Octane : 0.32 Tetradecene methyl- : 2.60 Toluene 7.93 7.56 Cyclohexane 2.28 2.51 1-Hexene 1.05 1.10 1-Hexene 1.15 1.16 Pentane : 1.95 Nonane : 0.83 Ethylbenzen 15.07 11.29 Heptane, 4- 1.81 1.68 Heptane 1.26 1.35 Heptane 1.22 1.23 Butane, 2,2- Decane : 1.34 e methyl- dimethyl- : 0.47 1-Tridecene 0 0.14 2,2-Dimethyl- 0.63 0 1-Heptene 1.37 1.46 1-Heptene 1.32 1.35 Pentane,
    [Show full text]
  • Title Crystallization of Stereospecific Olefin Copolymers (Special Issue on Physical Chemistry) Author(S) Sakaguchi, Fumio; Kita
    Crystallization of Stereospecific Olefin Copolymers (Special Title Issue on Physical Chemistry) Author(s) Sakaguchi, Fumio; Kitamaru, Ryozo; Tsuji, Waichiro Bulletin of the Institute for Chemical Research, Kyoto Citation University (1966), 44(4): 295-315 Issue Date 1966-10-31 URL http://hdl.handle.net/2433/76134 Right Type Departmental Bulletin Paper Textversion publisher Kyoto University Crystallization of Stereospecifie Olefin Copolymers Fumio SAKAGUCHI,Ryozo KITAMARU and Waichiro TSUJI* (Tsuji Laboratory) Received August 13, 1966 The stereoregularity of isotactic poly(4-methyl-1-pentene) was characterized and isomorphism phenomena were examined for the copolymeric systems of 4-methyl-1-pentene with several olefins in order to study the crystallization phenomena in these olefin copoly- mers polymerized with stereospecific catalysts. The structural heterogeneity or the fine crystalline structure of poly(4-methyl-1-pentene) could be correlated with its molecular structure by viewing this stereoregular homopolymer as if it were a copolymer. Cocrystallization or isomorphism phenomenon was recognized for the copolymeric systems of 4-methyl-1-pentene with butene-1, pentene-1, decene-1 and 3-methyl-1-butene, while no evidence of the phenomenon was obtained for the copolymeric systems with styrene and propylene. The degree of the isomorphism of those copolymers was discussed with the informations on the crystalline phases obtained from the X-ray study, on the constitution of the copolymeric chains in the amorphous phases obtained from the viscoelastic studies and on the other thermodynamical properties of these systems. INTRODUCTION Many works have been made with regard to the homopolymerization of olefins with stereospecific catalysts, i. e. complex catalysts composed of the combination of organometallic compound and transitional metallic compound.
    [Show full text]
  • Highly Efficient Olefin Isomerization Catalyzed by Metal Hydrides Derives from Dirhodium(Ii) Carboxylates and Catecholborane
    HIGHLY EFFICIENT OLEFIN ISOMERIZATION CATALYZED BY METAL HYDRIDES DERIVES FROM DIRHODIUM(II) CARBOXYLATES AND CATECHOLBORANE Gene A. Devora and Michael P. DoyleL' * Department of Chemistry, Trinity University, San Antonio, Texas 78212, USA Abstract. Dirhodium(ll) tetraacetate in combination with catecholborane catalyzes the iso- merization of alkenes and dienes. Effective isomerization occurs at 80-135°C with the use of only 0.1 mol % rhodium acetate. With 2-methyl-1,5-hexadiene the disubstituted double bond is prefer- entially isomerized. In addition, hydrogen transfer hydrogenation occurs with 1,4-cyclohexadienes. The mechanism of these reactions is proposed to involve organoborane addition across a Rh-0 bond which activates the catalyst for isomerization and hydrogenation. INTRODUCTION Catalytic isomerization of alkenes is a characteristic transformation of transition metal hy- drides that often accompanies hydrogenation1 and is one of the most thoroughly studied catalytic reactions.2"4 Compounds of cobalt, nickel, palladium, platinum, rhodium, and ruthenium are effective,2 but other transition metal compounds have also been employed for catalytic isomeriza- tions.2"4 Although the nature of this transformation is dependent on the catalyst, selectivity for alkene isomerization generally favors reactions with monosubstituted ethylenes over di- and tri-sub- stituted ethylenes. In the course of our investigations of the catalytic effectiveness of dirhodium(ll) tetrakis(carboxylates) we have uncovered a useful methodology for the generation of rhodium hydride species that, as we now report, are surprisingly effective for the isomerization of alkenes as well as for hydrogen transfer hydrogenation. MATERIALS AND METHODS Reactions were performed in a round bottom flask equipped with a screw cap that was fitted with a septum for convenient withdrawal of aliquots.
    [Show full text]
  • September 17, 2007
    Pre-Feasibility Report M/s. Neogen Chemicals Ltd. 1 1. Introduction M/s. Neogen Chemicals Ltd. is a new unit located at Plot No. Z/96/B SEZ Dahej, District: Bharuch, Gujarat. Now, the unit proposes to manufacture different type of synthetic organic dyes and pesticide products at above sited address. 2. Cost of Project Cost of existing project is 55 crore &, out of which 5 crore will be used for Environment Management System. 3. Production Capacity Production capacity is prescribe below: List of Products Sr. Name of Products Quantity No. (MT/Year) (MT/month) 1 Bromination and Chlorination of Alcohols 1.1. Ethyl Bromide 3500 291.67 1.2. n-Propyl Bromide 1.3. Iso Propyl Bromide 1.4. n-Butyl Bromide 1.5. Iso Butyl Bromide 1.6. Sec-Butyl Bromide 1.7. n-Hexyl Bromide 1.8. n-Heptyl Bromide 1.9. n-Octyl Bromide 1.10. n-Decyl Bromide 1.11. Lauryl Bromide 1.12. Cetyl Bromide 1.13. Myristyl Bromide 1.14. Stearyl Bromide 1.15. 1,2 Dibromo Ethane 1.16. 1,3 Dibromo Propane 1.17. 1,4 Dibromo Butane 1.18. 1,5 Dibromo pentane M/s. Neogen Chemicals Ltd. 2 Sr. Name of Products Quantity No. (MT/Year) (MT/month) 1.19. 1,6 Dibromo Hexane 1.20. 1 Chloro 2 Ethyl Hexane 1.21. 6 Chloro 1 Hexanol 1.22. 3 Chloro Propanol 1.23. 1,6 Dichloro Hexane 1.24. Cyclo Propyl Methyl Bromide 1.25. Cyclo Pentyl Bromide 1.26. Cyclo Pentyl Chloride 2. Bromination of Organic Acids and Esterification thereof 2.1.
    [Show full text]
  • ' United "States Patent Office
    Patented on. 20, 1.942 I . 2,299,411 ' UNITED "STATES PATENT OFFICE CATALYZED HYDROBROMINATION OF UN SATURATED ORGANIC COMPOUNDS Fredericlr Rust and William E. Vaughan, ' Berkeley, Calif., assignors. to Shell Develop ment Company, San Francisco, Calif., a corpo ration of Delaware No Drawing. 4 Application August 25, 1941, Serial No. 408,212 - 9'Claims. (01. 260-663) ' This invention relates to an improved process for the hydrobromination of unsaturated organic hydes and metal alkyls which tend to initiate I compounds, and more particularly to improve the reaction chains. v ments in the method of controlling the addition It is known that the presence of peroxide: orv of hydrogen bromide to unsymmetrical organic of peroxide-forming compounds in unsaturated compounds containing at least one ole?nic or organic compounds, e. g. unsaturated hydrocar acetylenic linkage to produce addition products bons, is undesirable. For example, organic per of a predetermined character. oxides, when present even in relatively small con It is known that hydrogen halides may be centrations, tend to catalyze the polymerization of a large number of unsaturated hydrocarbons, . added to unsaturated hydrocarbons and to var 10 ious unsaturated derivatives thereof. In fact, and particularly diole?ns. As to the “abnormal” in 1870 Markowniko? stated that “if an addition ofhydrogen bromide to unsaturates by metrical hydrocarbon combines with a halogen effecting the reaction under the deliberate in acid, the halogen adds to the carbon atom with ?uence, of light, and particularly of ultra-violet fewer hydrogen atoms, i. e. to the carbon atom radiations having wave-lengths of below about which is more'under the in?uence of other car' 2900 to 3000 Angstrom units, such processes ne bon atoms.” The same investigator further de cessitate the use of special equipment, such as termined that when a hydrogen halide is added reaction vessels provided with or containing to a halogenated unsaturated compound such as lamps made of quartz Or other suitable mate rials, e.
    [Show full text]
  • Chemical Compatibility Chart X
    Chemical Compatibility Chart Below is a chart adapted from the CRC Laboratory Handbook, which groups various chemicals in to 23 groups with examples and incompatible chemical groups. This chart is by no means complete but it will aid in making decisions about storage. For more complete information please refer to the MSDS for the specific chemical. Examples of each group can be found on the next pages. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Monomers Polymerizable Esters Alcohols, Glycols, Glycol Ether Amines and Alkanolamines Halogenated Compounds Aldehydes Acetaldehyde Saturated Hydrocar Aromatic Hydrocarbons Acid Anhydrides Alkylene Oxides Inorganic Acids Petrolium Oils Organic Acids Cyanohydrins Phosphorus Ammonia Group Halogens Ketones Caustics Phenols Nitriles Olefins Ethers Number/Chemical Esters Type bons Inorganic 1 x x x x x x x x x x x x x x x x x Acids 2 Organic Acids x x x x x x x x x x 3 Caustics x x x x x x x x x x x x x Amines and 4 x x x x x x x x x x x x Alkanolamines Halogenated 5 x x x x x x Compounds Alcohols, 6 Glycols, Glycol x x x x x x Ether Aldehydes 7 x x x x x x x x x x x x Acetaldehyde 8 Ketones x x x x x x Saturated 9 x Hydrocarbons Aromatic 10 x x Hydrocarbons 11 Olefins x x x 12 Petrolium Oils x 13 Esters x x x x x Monomers 14 Polymerizable x x x x x x x x x x x x Esters 15 Phenols x x x x x x x Alkylene 16 x x x x x x x x x x x x Oxides 17 Cyanohydrins x x x x x x x x x 18 Nitriles x x x x x x 19 Ammonia x x x x x x x x x x x 20 Halogens x x x x x x x x x x x x x x 21 Ethers x x x 22 Phosphorus x x x x Acid 23 x x x x x x x x x x Anhydrides X - Indicates chemicals that are incompatible and should not be stored together.
    [Show full text]
  • Table S1. GC-MS Compounds Generated at 5 °C/Min
    Table S1. GC-MS compounds generated at 5 °C/min. 0 wt.% 10 wt.% 30 wt.% 50 wt.% GC GC GC GC Compounds Compounds Compounds Compounds Area (%) Area (%) Area (%) Area (%) Time (min.) (min.) Time Time (min.) (min.) Time (min.) Time (min.) Time Propene Propene Propene Propene 7.42 7.42 1.26 5.47 1.20 7.38 1.200 1.200 1.200 1.214 1.214 1-Propene, 2- 1-Propene, 2- methyl- 1-Propene, 2-methyl- 1-Propene, 2-methyl- 7.34 7.34 2.41 methyl- 1.245 1.245 1.245 1.259 1.259 10.54 1.246 14.90 Pentane Pentane Pentane Pentane 3.79 3.79 1.375 1.375 1.395 1.395 11.81 1.381 13.17 1.375 12.83 1-Pentene, 2- 2-Butene, 2- 2-Butene, 2-methyl- 2-Butene, 2-methyl- methyl- 7.25 0.93 methyl- 4.65 5.71 1.426 1.426 1.420 1.420 1.679 1.679 1H-Pyrazole, 4,5- Heptane, 4- 1H-Pyrazole, 4,5- 1-Pentene, 2-methyl- dihydro-5- methyl- 1.92 1.57 2.25 dihydro-5-methyl- 2.44 1.659 1.659 1.562 1.569 3.762 3.762 methyl- 2,4-Dimethyl-1- 1-Pentene, 2- heptene 2-Butene, 2,3-dimethyl- 1-Pentene, 2-methyl- 1.27 1.27 methyl- 3.08 2.33 1.653 1.653 1.653 5.671 5.671 34.57 1.750 Cyclohexane, 1,3,5-trimethyl-, 2-Pentene, 3- 2,4-Dimethyl-1-heptene 2-Pentene, 2-methyl- alpha.,3.alpha.,5.b 2.03 9.11 methyl-, €- 6.11 5.73 5.605 5.605 1.743 1.744 5.981 5.981 eta.)- 5-Aminoisoxazole 2-Pentene, 3- 2-Pentene, 3-methyl-, Spermine Ethanone, 1-cyclopentyl- 1.55 1.55 1.32 methyl-, (Z)- 1.59 €- 1.46 1.828 1.828 1.828 6.925 6.925 10.560 Ethanone, 1- 1R,2c,3t,4t-Tetramethyl- 1,3-Pentadiene, 1,4-Hexadiene, 5- cyclopentyl- 3.57 3.57 cyclohexan 0.97 2,3-dimethyl- 2.28 methyl- 2.31 2.584 2.584 2.585 10.613 10.613 10.638 N- Heptane, 2-methyl-3- Heptane, 4- Methylallylamine Toluene 2.49 2.49 methylene- 2.50 methyl- 2.97 4.31 3.697 3.697 3.697 14.047 14.047 10.684 10.684 2-Undecene, 4- Cyclopentane, (2- 2,4-Dimethyl-1- 2,4-Dimethyl-1- methyl- 7.81 7.81 methylbutyl)- 1.00 heptene heptene 5.605 5.605 22.29 22.29 5.605 12.95 14.086 14.086 14.163 Cyclohexane, Cyclohexane, 1,3,5- 2-Decene, 7- 1,3,5-trimethyl-, trimethyl- methyl-, (Z)- Hexane, 2,3,4-trimethyl- (1.
    [Show full text]
  • Linear Alpha-Olefins (681.5030)
    IHS Chemical Chemical Economics Handbook Linear alpha-Olefins (681.5030) by Elvira O. Camara Greiner with Yoshio Inoguchi Sample Report from 2010 November 2010 ihs.com/chemical November 2010 LINEAR ALPHA-OLEFINS Olefins 681.5030 B Page 2 The information provided in this publication has been obtained from a variety of sources which SRI Consulting believes to be reliable. SRI Consulting makes no warranties as to the accuracy completeness or correctness of the information in this publication. Consequently SRI Consulting will not be liable for any technical inaccuracies typographical errors or omissions contained in this publication. This publication is provided without warranties of any kind either express or implied including but not limited to implied warranties of merchantability fitness for a particular purpose or non-infringement. IN NO EVENT WILL SRI CONSULTING BE LIABLE FOR ANY INCIDENTAL CONSEQUENTIAL OR INDIRECT DAMAGES (INCLUDING BUT NOT LIMITED TO DAMAGES FOR LOSS OF PROFITS BUSINESS INTERRUPTION OR THE LIKE) ARISING OUT OF THE USE OF THIS PUBLICATION EVEN IF IT WAS NOTIFIED ABOUT THE POSSIBILITY OF SUCH DAMAGES. BECAUSE SOME STATES DO NOT ALLOW THE EXCLUSION OR LIMITATION OF LIABILITY FOR CONSEQUENTIAL OR INCIDENTAL DAMAGES THE ABOVE LIMITATION MAY NOT APPLY TO YOU. IN SUCH STATES SRI CONSULTING’S LIABILITY IS LIMITED TO THE MAXIMUM EXTENT PERMITTED BY SUCH LAW. Certain statements in this publication are projections or other forward-looking statements. Any such statements contained herein are based upon SRI Consulting’s current knowledge and assumptions about future events including without limitation anticipated levels of global demand and supply expected costs trade patterns and general economic political and marketing conditions.
    [Show full text]
  • Ionic Liquid*
    Pure Appl. Chem., Vol. 83, No. 7, pp. 1391–1406, 2011. doi:10.1351/PAC-CON-10-12-03 © 2011 IUPAC, Publication date (Web): 10 June 2011 Oligomerisation of linear 1-olefins using a chlorogallate(III) ionic liquid* Martin P. Atkins1, Kenneth R. Seddon2,‡, and Małgorzata Swadźba-Kwaśny2,‡ 1PETRONAS Research Sdn Bhd, Lot 3288&3289, Off Jalan Ayer Itam, Kawasan Institusi Bangi, 43000, Kajang, Malaysia; 2QUILL, The Queen’s University of Belfast, Belfast, BT9 5AG, UK Abstract: A Lewis acidic chlorogallate(III) ionic liquid, 1-ethyl-3-methylimidazolium hepta - chlorodigallate(III), [C2mim][Ga2Cl7], was successfully used to oligomerise 1-pentene. The influence of temperature, time, catalyst concentration, and stirring rate on conversion and product distribution was modelled using a design of experiment (DoE) approach (chemo - metrics). The process was optimised for lubricant base oils production; the C20–C50 fraction (where Cn indicates the number of carbons in the oligomer) was maximised, while the heav- ier oligomer fraction (>C50) was minimised. Keywords: 1-alkenes; chemometrics; ionic liquids; linear terminal olefins; 1-olefins; oligomerisation. INTRODUCTION Oligomerisation and ionic liquids Polyalphaolefins (PAOs), used as a base for synthetic automotive lubricants (Group 4 base stock by API classification) [1], are traditionally made by oligomerisation of 1-decene to C20–C50 blend (where Cn indicates the number of carbons in the oligomer) [2] using Ziegler–Natta or Friedel–Crafts catalysts [3]. The carbon number is important, as the pour point of higher polymers (>C50) is too high, whilst the lower cut (<C20) is too volatile. 1-Decene is manufactured in a very selective manner from ethene [2].
    [Show full text]
  • Synthetic Applications of Organoboranes
    ú 7lt) f SYNTHETIC APPLICATIONS OF ORGANOBORANES A Thesis Presented for the Degree of Doctor of Philosophy in The Uníversity of Adelaide by Roger Murphy, B.Sc. (Hons.) Department of Organíc Chemistry L976. CONTENTS Page SUMMARY (f) STATEMENT (fií) PUBL ICATIONS (iv) ACKNOI^JLEDGEMENTS (v) CHAPTER 1. Synthesis of Products Isolated from the Hydroboration-Cyanidation of Unsaturated Terpenes. / 1.1 Introduction. 1 L.2 Synthesis of Products Derived from L2 Geraniol. 1.3 Synthesis of Products Derived from L7 LÍnalyl AceËate. L.4 SynthesÍs of Products Derived from 22 Myrcene. CHAPTER 2. Cyanidation of Dialkyìboranes and Borinic Acids and Esters. 2.L Introduction. 43 2.2 Cyanidation of Dialkylboranes. 50 2.3 Cyanidation of BorÍnic Acíds and EsËers. 65 CHAPTER 3. Silver(I) 0xidation of Organoboranes. 3.1 Introduction. 70 3.2 Cycl-izatlon of Díenes vía Intramolecular 76 Alkyl Coupling. 3.3 AÈtenpted Reduction of Intemedl-ates 84 Obtaíned by Reaction of Organoboranes with Alkalíne SÍ1ver nltrate. CHAPTER 4. Asymmetric Induction by Hydroboration with Optical ly Active Dial llyl boranes. 4.L Introductlon. 88 4.2 AËterpted Resolution of (t)-414,6- 96 Trfnethylcaprolactam and (t)-4 16 16- Tr lmethylcapro lactam. 4.3 Attempted Resolutíon of (1)-31515- 100 Trinethylcyclohexanone . 4.4 Asynrmetric Hydroboratfon of 6r7-Dihydro- 110 416 r6-trTmethyl-5H-azepínone and 3r5,5- TrirneËhylcyclohex-2-enone (Isophorone) . CHAPTER 5. Experimental. 5.1 General. 118 5.2 I^Iork described in chapter 1. L2T 5.3 Ilork described in chapter 2. 163 5.4 Work descríbed ín chapËer 3. 178 5.5 lJork described Ín chapter 4.
    [Show full text]
  • Light Linear Alpha Olefin Market Study
    IHS CHEMICAL Light Linear Alpha Olefin Market Study Special Report Prospectus IHS CHEMICAL Contents Contents ..................................................................................................................................... 2 Introduction ................................................................................................................................ 3 Study Scope ............................................................................................................................... 5 Key Questions Addressed in the Study ...................................................................................... 7 Deliverables ............................................................................................................................... 8 Proposed Table of Contents ...................................................................................................... 9 Methodology ............................................................................................................................ 11 Study Team .............................................................................................................................. 15 Qualifications............................................................................................................................ 18 About IHS Chemical ................................................................................................................. 21 About IHS ................................................................................................................................
    [Show full text]
  • JUN I 13998 Scienct LIBRARIES This Doctoral Thesis Has Been Examined by a Committee of the Department of Chemistry As Follows
    THE DEVELOPMENT OF ORGANOTIN REAGENTS FOR ORGANIC SYNTHESIS by David Scott Hays B. S. Chemistry, University of Illinois Submitted to the Department of Chemistry in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY IN ORGANIC CHEMISTRY at the Massachusetts Institute of Technology June 1998 © Massachusetts Institute of Technology, 1998 All rights reserved Signature of Author Department of Chemistry May 14, 1998 Certified by Gregory C. Fu t' Thesis Supervisor Accepted by Dietmar Seyferth Chairman, Departmental Committee on Graduate Students JUN I 13998 scienct LIBRARIES This doctoral thesis has been examined by a committee of the Department of Chemistry as follows: Professor Peter H. Seeberger I_ _ /1 Chairman Professor Gregory C. Fu J _J Thesis Supervisor Professor Rick L. Danheiser THE DEVELOPMENT OF ORGANOTIN REAGENTS FOR ORGANIC SYNTHESIS by David Scott Hays Submitted to the Department of Chemistry on May 14, 1998 in partial fulfillment of the requirements for the Degree of Doctor of Philosophy at the Massachusetts Institute of Technology ABSTRACT A method for the intramolecular pinacol coupling of dialdehydes and ketoaldehydes is described. The method was found to be useful for synthesizing 1,2-cyclopentanediols with very high degrees of diastereoselectivity in favor of the cis stereochemistry. 1,2- Cyclohexanediols were generated with lower degrees of stereoselection. This free radical chain process involves as the key steps: 1) an intramolecular addition of a tin ketyl radical to a pendant carbonyl group, followed by 2) a rapid intramolecular homolytic displacement by an oxygen radical at the tin center to liberate an alkyl radical. The development of a Bu 3 SnH-catalyzed carbon-carbon bond forming reaction (the reductive cyclization of enals and enones) is described, followed by a catalytic variant of the Barton-McCombie deoxygenation reaction.
    [Show full text]