DOCSLIB.ORG

United States Patent (19) 11) 4,224,426 Odar 45) Sep

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
United States Patent (19) 11) 4,224,426 Odar 45) Sep United States Patent (19) 11) 4,224,426 Odar 45) Sep. 23, 1980 (54) POLYMERIZATION PROCESS FOR 3,222,347 12/1965 Farrar et al. CIS-1,4-POLYBUTADIENE USING 3,222,348 12/1965 Duck . CYCLOALKANE SOLVENTS AND AN 3,284,431 11/1966 Gippin . AROMATIC POLYMERIZATION 3,331,826 7/1967 Talcott ............................... 526/335 REGULATOR 3,646,001 2/1972 Lasis et al. 3,928,303 12/1975 Yasui et al. .......................... 526/335 75 Inventor: Joseph Odar, South Euclid, Ohio FOREIGN PATENT DOCUMENTS 73) Assignee: The B. F. Goodrich Company, Akron, 924427 4/1963 United Kingdom. Ohio 926036 5/1963 United Kingdom. 21 Appl. No.: 960,388 Primary Examiner-Harry Wong, Jr. 22) Filed: Nov. 13, 1978 Attorney, Agent, or Firm--Nestor W. Shust (51) Int. Cl’.............................................. CO8F 36/06 57 ABSTRACT (52) U.S. C. ....................................... 526/92; 526/335 Substantially gel-free cis-1,4-polybutadiene is produced 58) Field of Search .................................. 526/335, 92 by polymerizing butadiene in the presence of a catalyst comprising a mixture of a cobalt compound, at least one (56) References Cited organoaluminum compound and water, the improve U.S. PATENT DOCUMENTS ment being the use of a cycloalkane having 5 to 8 car 2,999,089 9/1961 Short et al. bon atoms in the ring and from 0.1 to 2 percent of an 3,046,265 7/1962 Hazen et al. alkyl substituted benzene as a polymerization regulator. 3,094,514 6/1963 Tucker . 3,135,725 6/1964 Carlson et al. 12 Claims, No Drawings 4,224,426 1. 2 POLYMERIZATION PROCESS FOR SUMMARY OF THE INVENTION CIS-1,4-POLYBUTADIENE USING The polymerization of butadiene-1,3 is carried out in CYCLOALKANE SOLVENTS AND ANAROMATIC the presence of a catalyst comprising a mixture of cobalt POLYMERIZATION REGULATOR 5 compound, an organoaluminum compound and water. The present invention deals with the improvement in BACKGROUND OF THE INVENTION the process of butadiene polymerization the improve ment being the use as a solvent a cycloaliphatic hydro Polymerization of conjugated dienes, especially carbon and from 0.1 to 2% by weight of an alkyl sub butadiene-1,3, is well known in the art using a variety of 10 stituted benzene to produce substantially linear gel-free catalysts and a variety of solvents. Thus U.S. Pat. No. cis-1,4-polybutadiene. 3,135,725 discloses cobalt salt-hydrocarbyl aluminum catalysts and U.S. Pat. No. 3,046,265 discloses alkyl DETAILED DISCLOSURE aluminum, cobalt halide and acetyl halide catalysts, This invention is directed to an improved process of both employing a variety of diluents including aliphatic, 15 polymerizing butadiene-1,3 to produce primarily linear, cycloaliphatic and aromatic hydrocarbons. U.S. Pat. gel-free cis-1,4-polybutadiene. More specifically, the Nos. 3,094,514 and 3,646,001 even suggest the use of a improved process is carried out in the presence of a mixture of aliphatic and aromatic hydrocarbons but catalyst comprising a mixture of a cobalt compound, at clearly stating that the mixture must contain at least least one organoaluminum compound and water, the 15% by weight of an aromatic solvent. The former 20 improvement which comprises using as a solvent a cy patent notes that the presence of the aromatic hydrocar cloalkane having 5 to 8 carbon atoms in the ring and bon produces somewhat faster reactions. from 0.1 to 2 percent, based on the weight of cycloal Although generally the order of addition of the reac kane, of an alkyl substituted benzene as a polymeriza tants and the catalysts apparently was not considered to tion regulator. be of critical importance, various patents disclose differ 25 It was unexpectedly found that when a cycloalkane ent orders of addition. Thus in British Pat. No. 926,036 was used as the chief solvent in the polymerization of the reactants and catalysts were added in the order of a butadiene, the polymerization proceeded at too fast a solvent, an aluminum compound, cobalt chloride in rate as a result of which it was difficult to control the pyridine and finally butadiene while in British Pat. No. polymerization temperature. The resulting cis 924,427 the order was: an aromatic solvent, cobalt and 30 polybutadiene possessed a higher degree of vinyl con then aluminum compounds as catalysts, an additional tent and did not possess the desired physical properties. aromatic solvent, an aliphatic solvent and finally butadi It was also unexpectedly found that a small amount of ene. U.S. Pat. No. 3,284,431 discloses adding to the an alkyl substituted benzene substantially slowed down reaction vessel an aromatic solvent, butadiene, an alumi the initial rate of polymerization so that it could be 35 easily controlled. This was unexpected since prior art num compound catalyst, an activator and finally a co taught that butadiene polymerization proceeds faster in balt compound catalyst. Another order of addition is an aromatic solvent than in a non-aromatic solvent (e.g. disclosed in U.S. Pat. No. 3,646,001 where cobalt and U.S. Pat. No. 3,094,514). Thus the present invention is aluminum catalysts, such as cobalt octoate and diethyl an improved process of butadiene-1,3 polymerization aluminum chloride, are prereacted in wet benzene at a employing a cycloalkane solvent and from 0.1 to 2 per temperature below 20 C. and then are added butadiene cent by weight of an alkyl substituted benzene as a and additional solvents such as benzene and butene-l. polymerization regulator. Therefore the process of the Published Japanese patent application SHO-44-10276 present invention successfully eliminates the need for discloses dissolving a cobalt catalyst in dry toluene, benzene yet yields substantially linear, gel-free cis-1,4- feeding butadiene-1,3 to the reaction vessel and then 45 polybutadiene having good physical properties. adding an aluminum catalyst to begin polymerization. Cycloalkanes useful in the process are those having 5 As a rule the most preferred solvent for butadiene to 8 carbon atoms in the rings. They also include methyl polymerization has been benzene. However, from the and ethyl substituted cycloalkanes. Illustrative exam point of view of health safety, benzene is an undesirable ples of cycloalkanes are cyclopentane, cyclohexane, material as evidenced by recent severe restrictions 50 cycloheptane, cyclooctane, methylcyclopentane, me placed by the Occupational Safety and Health Agency thylcyclohexane, methylcycloheptane, methylcyclooc (OSHA) on the concentration of benzene permissible in tane, dimethylcyclopentane, dimethylcyclohexane, the work area. For this reason it is imperative to find a dimethylcycloheptane, ethylcyclopentane, ethylcy solvent or solvent combinations for butadiene polymer clohexane, ethylcyclooctane and the like. Preferred are izations that would yield cis-1,4-polybutadiene having 55 unsubstituted and methyl substituted cycloalkanes. the same or better properties than those of polybutadi Most preferred, for economic reasons, is cyclohexane. ene prepared in benzene. The second critical component of the improved pro The difficulty with most solvents is, however, that cess, a polymerization regulator, is a lower alkyl sub the polymerization rate is too fast making the reaction stituted benzene having 1 to 4 alkyl substituents of 1 to practically uncontrollable, or it is too slow and there 60 4 carbon atoms. Preferably there are 2 or 3 methyl or fore not economically feasible. The initial rate of con ethyl substituents. Illustrative examples of the useful version (polymerization) of the monomer is of critical alkyl substituted benzenes are toluene, o, m or p-xylene importance since a difference of only a few percentage or a mixture of xylene isomers, 1,3,5-trimethylbenzene points may make the difference between having a con (mesitylene) and other isomers of trimethylbenzene, or trollable and an uncontrollable polymerization. Fur 65 a mixture thereof, 1,2,4,5-tetramethylbenzene (durene) thermore, if the polymer is formed at a certain polymer and other isomers of tetramethylbenzene, or a mixture ization rate it will not have the required desirable prop thereof, ethylbenzene, 1,2-, 1.3- or 1,4-diethylbenzene, erties. or a mixture of said isomers, n-propylbenzene, 1,4-n- 4,224,426 3 4. dipropylbenzene, n-butylbenzene and the like, or a mix organic portion of the molecule contains about 5 to 20, ture of various alkyl substituted benzenes. Preferred are preferably 8 to 18 carbon atoms and one or two carbox various xylene isomers or a mixture thereof, various ylic functions, as well as acetylacetonate, as are well diethylbenzene isomers or a mixture thereof and mesity known to those skilled in the art. lene. The alkyl substituted benzene is used in the The other essential catalyst component is an alkyl amount of from 0.1 to 1 percent by weight of the total aluminum halide which can be used as a mono- or dial charge, and preferably from 0.2 to 0.7 percent by kyl aluminum halide, a mixture thereof, or a mixture of weight. R3A1, R2A1X, RAIX2 or AlX3 type compounds wherein One of the purposes of a solvent in this process is to R is an alkyl and X is halogen, more preferably, the control the polymerization temperature by refluxing the 10 chloride. The alkyl groups normally contain 1 to 12 solvent. Often the desired temperature control is diffi carbon atoms, more preferably, about 2 to 8 carbon cult to accomplish with only one solvent. However, by atoms. Particularly useful are dialkyl aluminum chlo selecting two or more solvents which have certain de rides wherein the alkyl contains 2 to 6 carbon atoms, sirable boiling points, the polymerization temperature and the so-called sesquichloride which is a mixture of can be relatively easily controlled. Therefore, the selec 15 aluminum trichloride and trialkyl aluminum, normally tion of the secondary solvent will depend primarily on having a composition of about R1.5-1.9AlX1.6-1.1.
Load more

Recommended publications
  • C9-14 Aliphatic [2-25% Aromatic] Hydrocarbon Solvents Category SIAP
    CoCAM 2, 17-19 April 2012 BIAC/ICCA SIDS INITIAL ASSESSMENT PROFILE Chemical C -C Aliphatic [2-25% aromatic] Hydrocarbon Solvents Category Category 9 14 Substance Name CAS Number Stoddard solvent 8052-41-3 Chemical Names Kerosine, petroleum, hydrodesulfurized 64742-81-0 and CAS Naphtha, petroleum, hydrodesulfurized heavy 64742-82-1 Registry Solvent naphtha, petroleum, medium aliphatic 64742-88-7 Numbers Note: Substances in this category are also commonly known as mineral spirits, white spirits, or Stoddard solvent. CAS Number Chemical Description † 8052-41-3 Includes C8 to C14 branched, linear, and cyclic paraffins and aromatics (6 to 18%), <50ppmV benzene † 64742-81-0 Includes C9 to C14 branched, linear, and cyclic paraffins and aromatics (10 to Structural 25%), <100 ppmV benzene Formula † and CAS 64742-82-1 Includes C8 to C13 branched, linear, and cyclic paraffins and aromatics (15 to 25%), <100 ppmV benzene Registry † Numbers 64742-88-7 Includes C8 to C13 branched, linear, and cyclic paraffins and aromatics (14 to 20%), <50 ppmV benzene Individual category member substances are comprised of aliphatic hydrocarbon molecules whose carbon numbers range between C9 and C14; approximately 80% of the aliphatic constituents for a given substance fall within the C9-C14 carbon range and <100 ppmV benzene. In some instances, the carbon range of a test substance is more precisely defined in the test protocol. In these instances, the specific carbon range (e.g. C8-C10, C9-C10, etc.) will be specified in the SIAP. * It should be noted that other substances defined by the same CAS RNs may have boiling ranges outside the range of 143-254° C and that these substances are not covered by the category.
    [Show full text]
  • Cycloalkanes, Cycloalkenes, and Cycloalkynes
    CYCLOALKANES, CYCLOALKENES, AND CYCLOALKYNES any important hydrocarbons, known as cycloalkanes, contain rings of carbon atoms linked together by single bonds. The simple cycloalkanes of formula (CH,), make up a particularly important homologous series in which the chemical properties change in a much more dramatic way with increasing n than do those of the acyclic hydrocarbons CH,(CH,),,-,H. The cyclo- alkanes with small rings (n = 3-6) are of special interest in exhibiting chemical properties intermediate between those of alkanes and alkenes. In this chapter we will show how this behavior can be explained in terms of angle strain and steric hindrance, concepts that have been introduced previously and will be used with increasing frequency as we proceed further. We also discuss the conformations of cycloalkanes, especially cyclo- hexane, in detail because of their importance to the chemistry of many kinds of naturally occurring organic compounds. Some attention also will be paid to polycyclic compounds, substances with more than one ring, and to cyclo- alkenes and cycloalkynes. 12-1 NOMENCLATURE AND PHYSICAL PROPERTIES OF CYCLOALKANES The IUPAC system for naming cycloalkanes and cycloalkenes was presented in some detail in Sections 3-2 and 3-3, and you may wish to review that ma- terial before proceeding further. Additional procedures are required for naming 446 12 Cycloalkanes, Cycloalkenes, and Cycloalkynes Table 12-1 Physical Properties of Alkanes and Cycloalkanes Density, Compounds Bp, "C Mp, "C diO,g ml-' propane cyclopropane butane cyclobutane pentane cyclopentane hexane cyclohexane heptane cycloheptane octane cyclooctane nonane cyclononane "At -40". bUnder pressure. polycyclic compounds, which have rings with common carbons, and these will be discussed later in this chapter.
    [Show full text]
  • Introduction to Alkenes and Alkynes in an Alkane, All Covalent Bonds
    Introduction to Alkenes and Alkynes In an alkane, all covalent bonds between carbon were σ (σ bonds are defined as bonds where the electron density is symmetric about the internuclear axis) In an alkene, however, only three σ bonds are formed from the alkene carbon -the carbon thus adopts an sp2 hybridization Ethene (common name ethylene) has a molecular formula of CH2CH2 Each carbon is sp2 hybridized with a σ bond to two hydrogens and the other carbon Hybridized orbital allows stronger bonds due to more overlap H H C C H H Structure of Ethylene In addition to the σ framework of ethylene, each carbon has an atomic p orbital not used in hybridization The two p orbitals (each with one electron) overlap to form a π bond (p bonds are not symmetric about the internuclear axis) π bonds are not as strong as σ bonds (in ethylene, the σ bond is ~90 Kcal/mol and the π bond is ~66 Kcal/mol) Thus while σ bonds are stable and very few reactions occur with C-C bonds, π bonds are much more reactive and many reactions occur with C=C π bonds Nomenclature of Alkenes August Wilhelm Hofmann’s attempt for systematic hydrocarbon nomenclature (1866) Attempted to use a systematic name by naming all possible structures with 4 carbons Quartane a alkane C4H10 Quartyl C4H9 Quartene e alkene C4H8 Quartenyl C4H7 Quartine i alkine → alkyne C4H6 Quartinyl C4H5 Quartone o C4H4 Quartonyl C4H3 Quartune u C4H2 Quartunyl C4H1 Wanted to use Quart from the Latin for 4 – this method was not embraced and BUT has remained Used English order of vowels, however, to name the groups
    [Show full text]
  • 2: Alkanes and Cycloalkanes
    (2/94)(1,2,8/95)(6,7/97)(10/98)(1,9-11/99) Neuman Chapter 2 2: Alkanes and Cycloalkanes Alkanes Alkane Systematic Nomenclature Cycloalkanes Conformations of Alkanes Conformations of Cycloalkanes Conformations of Alkylcyclohexanes Preview You learned in the Chapter 1 that all organic molecules have carbon skeletons. These carbon skeletons show great diversity in the ways that C atoms bond to each other, and in their three-dimensional shapes. Alkanes and cycloalkanes consist entirely of carbon skeletons bonded to H atoms since they have no functional groups. As a result, they serve as a basis for understanding the structures of all other organic molecules. This chapter describes the skeleltal isomerism of alkanes and cycloalkanes, their three-dimensional conformations, and their systematic nomenclature that is the basis for the names of all other organic compounds. 2.1 Alkanes We refer to alkanes as hydrocarbons because they contain only C (carbon) and H (hydrogen) atoms. Since alkanes are the major components of petroleum and natural gas, they often serve as a commercial starting point for the preparation of many other classes of organic molecules. Structures of Alkanes (2.1A) Organic chemists use a variety of different types of structures to represent alkanes such as these shown for methane (one C), ethane (two C's), and propane (three C's). [graphic 2.1] Kekulé, Electron-Dot and Three-Dimensional Structures. The structures showing C and H atoms connected by lines are Kekulé structures. Remember from Chapter 1 that these lines represent chemical bonds that are pairs of electrons located in molecular orbitals encompassing the two bonded atoms.
    [Show full text]
  • 2.5 Cycloalkanes and Skeletal Structures 67
    02_BRCLoudon_pgs4-4.qxd 11/26/08 8:36 AM Page 67 2.5 CYCLOALKANES AND SKELETAL STRUCTURES 67 Likewise, the hydrogens bonded to each type of carbon are called primary, secondary, or ter- tiary hydrogens, respectively. primary hydrogens CH3 CH3 H3C CH2 CH2 "CH "C CH3 L L L LL L "CH primary hydrogens secondary hydrogens 3 tertiary hydrogen PROBLEMS 2.10 In the structure of 4-isopropyl-2,4,5-trimethylheptane (Problem 2.9) (a) Identify the primary, secondary, tertiary, and quaternary carbons. (b) Identify the primary, secondary, and tertiary hydrogens. (c) Circle one example of each of the following groups: a methyl group; an ethyl group; an isopropyl group; a sec-butyl group; an isobutyl group. 2.11 Identify the ethyl groups and the methyl groups in the structure of 4-sec-butyl-5-ethyl-3- methyloctane, the compound discussed in Study Problem 2.5. Note that these groups are not necessarily confined to those specifically mentioned in the name. 2.5 CYCLOALKANES AND SKELETAL STRUCTURES Some alkane contain carbon chains in closed loops, or rings; these are called cycloalkanes. Cycloalkanes are named by adding the prefix cyclo to the name of the alkane. Thus, the six- membered cycloalkane is called cyclohexane. CH2 H C CH 2 M % 2 H2""C CH2 %CHM2 cyclohexane The names and some physical properties of the simple cycloalkanes are given in Table 2.3. The general formula for an alkane containing a single ring has two fewer hydrogens than that of the open-chain alkane with the same number of carbon atoms.
    [Show full text]
  • Chem 341 • Organic Chemistry I Lecture Summary 10 • September 14, 2007
    Chem 341 • Organic Chemistry I Lecture Summary 10 • September 14, 2007 Chapter 4 - Stereochemistry of Alkanes and Cycloalkanes Conformations of Cycloalkanes Cyclic compounds contain something we call Ring Strain. There are three things that contribute to ring strain. Torsional strain (electron repulsion in eclipsing bonds), steric strain (atoms bumping into each other) and angle strain. Angle Strain: the strain due to bond angles being forced to expand or contract from their ideal. Sp3 hybridized atoms want to have bond angles of 109.5°. However, if the rings are very small or very large, there is no way to accommodate this angle. Thus, this increases the energy of the molecule. Heat of Combustion: the amount of heat (energy) released when a molecule burns completely with oxygen. By comparing the heat of combustion of different sized cycloalkanes, their relative energies can be obtained. The fact that the size of the ring has an influence on the total energy of the molecule indicates that there is some degree of instability associated with constraining the rings. This added energy (in addition to what would be expected from carbon and hydrogen combustion per mole) can be attributed to ring strain. n i a r t S g n i R 3 4 5 6 7 8 9 10 11 12 13 14 Ring Size Conformations of Cyclopropane Cyclopropane has a high degree of angle strain due to the highly distorted bond angles. The angle between the carbons is 60°. This cannot be accommodated by sp3-hybridized atoms. Thus, the 60° bonds actually are bent sigma bonds.
    [Show full text]
  • Industrial Hydrocarbon Processes
    Handbook of INDUSTRIAL HYDROCARBON PROCESSES JAMES G. SPEIGHT PhD, DSc AMSTERDAM • BOSTON • HEIDELBERG • LONDON NEW YORK • OXFORD • PARIS • SAN DIEGO SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO Gulf Professional Publishing is an imprint of Elsevier Gulf Professional Publishing is an imprint of Elsevier The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK 30 Corporate Drive, Suite 400, Burlington, MA 01803, USA First edition 2011 Copyright Ó 2011 Elsevier Inc. All rights reserved No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means electronic, mechanical, photocopying, recording or otherwise without the prior written permission of the publisher Permissions may be sought directly from Elsevier’s Science & Technology Rights Department in Oxford, UK: phone (+44) (0) 1865 843830; fax (+44) (0) 1865 853333; email: [email protected]. Alternatively you can submit your request online by visiting the Elsevier web site at http://elsevier.com/locate/ permissions, and selecting Obtaining permission to use Elsevier material Notice No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein. Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drug dosages should be made British Library Cataloguing in Publication Data
    [Show full text]
  • Cyclohydrocarbons: Structural Formulas Cyclohydrocarbons: Nomenclature
    Cyclohydrocarbons: Structural Formulas Cyclohydrocarbons are the cyclic, or ring, analogues of the alkanes, alkenes, and alkynes. These hydrocarbons are often referred to as alicyclic compounds, and the simplest class is made up of the cycloalkanes. Their general molecular formula is C n H2 n , where n equals any whole number of 3 or greater. Normally, these compounds are represented by geometric figures. Cyclohydrocarbons: Nomenclature Substituted cycloalkanes are named in a manner similar to the openchain, or aliphatic, alkanes. The following rules summarize the International Union of Pure and Applied Chemistry (IUPAC) nomenclature for substituted cycloalkanes. 1. Determine the number of carbon atoms in the ring and in the largest substituent. If the ring has more carbons than the substituent, the compound is an alkyl-substituted cycloalkane. If the substituent possesses more carbons than the ring, the compound is a cycloalkyl alkane. 2. If an alkyl-substituted cycloalkane has more than one substituent, the ring is numbered so the substituents have the lowest sum of numbers. 3. If the molecule possesses two or more different substituent groups, the number one position is determined by alphabetical priority. Cyclohydrocarbons: Preparations Cycloalkanes can be prepared by ring-cyclization reactions, such as a modified Wurtz reaction or a condensation reaction. Additionally, they can be prepared from cycloalkenes and cycloalkynes (Figure 1 ). Figure 1 Cycloalkenes and cycloalkynes are normally prepared from cycloalkanes by ordinary alkene-forming reactions, such as dehydration, dehalogenation, and dehydrohalogenation. Typical preparations for cyclohexene and cyclohexyne are illustrated in Figure 2 . Figure 2 Cyclohydrocarbons: Reactions Due to angle strain, the bonds in three- and four-membered carbon rings are weak.
    [Show full text]
  • 1 Chapter 3: Organic Compounds: Alkanes and Cycloalkanes
    Chapter 3: Organic Compounds: Alkanes and Cycloalkanes >11 million organic compounds which are classified into families according to structure and reactivity Functional Group (FG): group of atoms which are part of a large molecule that have characteristic chemical behavior. FG’s behave similarly in every molecule they are part of. The chemistry of the organic molecule is defined by the function groups it contains 1 C C Alkanes Carbon - Carbon Multiple Bonds Carbon-heteroatom single bonds basic C N C C C X X= F, Cl, Br, I amines Alkenes Alkyl Halide H C C C O C C O Alkynes alcohols ethers acidic H H H C S C C C C S C C H sulfides C C thiols (disulfides) H H Arenes Carbonyl-oxygen double bonds (carbonyls) Carbon-nitrogen multiple bonds acidic basic O O O N H C H C O C Cl imine (Schiff base) aldehyde carboxylic acid acid chloride O O O O C C N C C C C O O C C nitrile (cyano group) ketones ester anhydrides O C N amide opsin Lys-NH2 + Lys- opsin H O H N rhodopsin H 2 Alkanes and Alkane Isomers Alkanes: organic compounds with only C-C and C-H single (s) bonds. general formula for alkanes: CnH(2n+2) Saturated hydrocarbons Hydrocarbons: contains only carbon and hydrogen Saturated" contains only single bonds Isomers: compounds with the same chemical formula, but different arrangement of atoms Constitutional isomer: have different connectivities (not limited to alkanes) C H O C4H10 C5H12 2 6 O OH butanol diethyl ether straight-chain or normal hydrocarbons branched hydrocarbons n-butane n-pentane Systematic Nomenclature (IUPAC System) Prefix-Parent-Suffix
    [Show full text]
  • Robust Summary for Petroleum Gases
    ROBUST SUMMARIES OF STUDIES USED TO CHARACTERIZE THE PETROLEUM GASES CATEGORY Submitted to the USEPA by The Petroleum HPV Testing Group www.petroleumhpv.org Consortium Registration # 1100997 October 19, 2009 1 Robust Summaries Of Studies Used To Characterize the Petroleum Hydrocarbon Gases Category Table of Contents Physico‐Chemical Data ................................................................................................................................................................................................... 4 MELTING POINT ......................................................................................................................................................................................................... 4 BOILING POINT ........................................................................................................................................................................................................... 8 VAPOR PRESSURE ..................................................................................................................................................................................................... 12 PARTITION COEFFICIENT .......................................................................................................................................................................................... 16 WATER SOLUBILITY .................................................................................................................................................................................................
    [Show full text]
  • WO 2007/135043 Al
    (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (43) International Publication Date (10) International Publication Number 29 November 2007 (29.11.2007) PCT WO 2007/135043 Al (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C07C 4/06 (2006.01) BOlJ 8/00 (2006.01) kind of national protection available): AE, AG, AL, AM, C07C 11/06 (2006.01) AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, CA, CH, CN, CO, CR, CU, CZ, DE, DK, DM, DZ, EC, EE, EG, ES, (21) International Application Number: FI, GB, GD, GE, GH, GM, GT, HN, HR, HU, ID, IL, IN, PCT/EP2007/054739 IS, JP, KE, KG, KM, KN, KP, KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, MG, MK, MN, MW, MX, MY, (22) International Filing Date: 16 May 2007 (16.05.2007) MZ, NA, NG, NI, NO, NZ, OM, PG, PH, PL, PT, RO, RS, RU, SC, SD, SE, SG, SK, SL, SM, SV, SY, TJ, TM, TN, (25) Filing Language: English TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW (26) Publication Language: English (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, (30) Priority Data: GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), 061 14272.5 19 May 2006 (19.05.2006) EP European (AT,BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, HU, IE, IS, IT, LT,LU, LV,MC, MT, NL, PL, (71) Applicant (for all designated States except US): SHELL PT, RO, SE, SI, SK, TR), OAPI (BF, BJ, CF, CG, CI, CM, INTERNATIONALE RESEARCH MAATSCHAPPIJ GA, GN, GQ, GW, ML, MR, NE, SN, TD, TG).
    [Show full text]
  • Baeyer's Angle Strain Theory for B.Sc. Sem-II Organic Chemistry: US02CCHE01 by Dr. Vipul B. Kataria Introduction
    Baeyer’s Angle Strain Theory For B.Sc. Sem-II Organic Chemistry: US02CCHE01 By Dr. Vipul B. Kataria Introduction Van’t Hoff and Lebel proposed tetrahedral geometry of carbon. The bond angel is of 109˚ 28' (or 109.5˚) for carbon atom in tetrahedral geometry (methane molecule). Baeyer observed different bond angles for different cycloalkanes and also observed some different properties and stability. On this basis, he proposed angle strain theory. The theory explains reactivity and stability of cycloalkanes. Baeyer proposed that the optimum overlap of atomic orbitals is achieved for bond angel of 109.5o. In short, it is ideal bond angle for alkane compounds. Effective and optimum overlap of atomic orbitals produces maximum bond strength and stable molecule. If bond angles deviate from the ideal then ring produce strain. Higher the strain higher the instability. Higher strain produce increased reactivity and increases heat of combustion. Baeyer proposed “any deviation of bond angle from ideal bond angle value (109.5o) will produce a strain in molecule. Higher the deviation lesser the instability”. Que.1 Discuss Baeyer’s angle strain theory using concept of angle strain. Baeyer’s theory is based upon some assumptions as following. 1. All ring systems are planar. Deviation from normal tetrahedral angles results in to instable cycloalkanes. 2. The large ring systems involve negative strain hence do not exists. 3. The bond angles in cyclohexane and higher cycloalkanes (cycloheptane, cyclooctane, cyclononane……..) are not larger than 109.5o because the carbon rings of those compounds are not planar (flat) but they are puckered (Wrinkled). 1 | Page These assumptions are helpful to understand instability of cycloalkane ring systems.
    [Show full text]