US20100298507A1 - Polyisobutylene Production Process With Improved Efficiencies And/Or For Forming Products Having Improved Characteristics And Polyisobutylene Products Produced Thereby - Google Patents
Polyisobutylene Production Process With Improved Efficiencies And/Or For Forming Products Having Improved Characteristics And Polyisobutylene Products Produced Thereby Download PDFInfo
- Publication number
- US20100298507A1 US20100298507A1 US12/468,195 US46819509A US2010298507A1 US 20100298507 A1 US20100298507 A1 US 20100298507A1 US 46819509 A US46819509 A US 46819509A US 2010298507 A1 US2010298507 A1 US 2010298507A1
- Authority
- US
- United States
- Prior art keywords
- diluent
- polyisobutylene
- product
- set forth
- admixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229920002367 Polyisobutene Polymers 0.000 title claims abstract description 130
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000003085 diluting agent Substances 0.000 claims abstract description 140
- 238000000034 method Methods 0.000 claims abstract description 90
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- 230000008569 process Effects 0.000 claims abstract description 80
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 70
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 68
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 239000001282 iso-butane Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- 230000001965 increasing effect Effects 0.000 claims description 20
- 230000007423 decrease Effects 0.000 claims description 14
- 230000003247 decreasing effect Effects 0.000 claims description 11
- 239000008139 complexing agent Substances 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 230000006872 improvement Effects 0.000 claims description 5
- 150000003138 primary alcohols Chemical class 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000008859 change Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 81
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000001542 size-exclusion chromatography Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- WETOLIQTOVLBSX-UVTDQMKNSA-N C/C=C(/C)CC(C)(C)CC(C)(C)CC(C)(C)C Chemical compound C/C=C(/C)CC(C)(C)CC(C)(C)CC(C)(C)C WETOLIQTOVLBSX-UVTDQMKNSA-N 0.000 description 1
- WETOLIQTOVLBSX-GXDHUFHOSA-N C/C=C(\C)CC(C)(C)CC(C)(C)CC(C)(C)C Chemical compound C/C=C(\C)CC(C)(C)CC(C)(C)CC(C)(C)C WETOLIQTOVLBSX-GXDHUFHOSA-N 0.000 description 1
- UANJDEPRRZDYGA-UHFFFAOYSA-N C=C(C)CC(C)(C)CC(C)(C)CC(C)(C)C Chemical compound C=C(C)CC(C)(C)CC(C)(C)CC(C)(C)C UANJDEPRRZDYGA-UHFFFAOYSA-N 0.000 description 1
- MWSHFESREKAWKZ-UHFFFAOYSA-N CC(C)=C(C)C(C)(C)CC(C)(C)CC(C)(C)C Chemical compound CC(C)=C(C)C(C)(C)CC(C)(C)CC(C)(C)C MWSHFESREKAWKZ-UHFFFAOYSA-N 0.000 description 1
- YJSQJYADFSVLHZ-UHFFFAOYSA-N CC(C)=CC(C)(C)CC(C)(C)CC(C)(C)C Chemical compound CC(C)=CC(C)(C)CC(C)(C)CC(C)(C)C YJSQJYADFSVLHZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 241000276498 Pollachius virens Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- -1 for example Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/08—Butenes
- C08F110/10—Isobutene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
- C08F4/14—Boron halides or aluminium halides; Complexes thereof with organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/08—Butenes
- C08F10/10—Isobutene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2400/00—Characteristics for processes of polymerization
- C08F2400/02—Control or adjustment of polymerization parameters
Definitions
- the invention described hereinafter relates to improvements in the polymerization of isobutylene.
- the invention relates to processes for preparing polyisobutylene (PIB) products having improved characteristics.
- the invention relates to techniques for manipulation and control of liquid phase processes for producing polyisobutylene, polyisobutylene products having pre-selected characteristics, and methodology which enhances the operation and control of polyisobutylene reactors.
- U.S. Pat. No. 6,562,913 issued on May 13, 2003 and entitled “Process for Producing High Vinylidene Polyisobutylene” (hereinafter the '913 patent) relates, inter alia, to liquid phase polymerization processes for preparing low molecular weight (number average molecular weight (M N ) less than about 10,000), highly reactive (terminal double bond content of at least about 70%) polyisobutylene products.
- M N number average molecular weight
- a catalyst composition which desirably may comprise a complex of BF 3 and complexing agent such as methanol, and a feedstock containing isobutylene, are each introduced into a reaction zone where the same are intimately admixed with residual reaction mixture so as to present an intimately intermixed reaction admixture in the reaction zone.
- the intimately intermixed reaction admixture is maintained in its intimately intermixed condition and at a relatively constant temperature of at least about 0° C. while the same is in the reaction zone, whereby isobutylene therein is polymerized to form a polyisobutylene product having a high degree of terminal (vinylidene) unsaturation.
- a crude product stream comprising residual catalyst composition, unreacted isobutylene and polyisobutylene is then withdrawn from the reaction zone.
- the introduction of feedstock into and the withdrawal of product stream from the reaction zone are each controlled such that the residence time of the isobutylene undergoing polymerization in the reaction zone is no greater than about 4 minutes, whereby the product stream contains a highly reactive polyisobutylene product.
- the reaction zone may be the tube side of a shell-and-tube exchanger in which a coolant is circulated on the shell side.
- a recirculation loop may desirably be employed to circulate the reaction admixture through the tube side reaction zone at a linear velocity sufficient to establish and maintain an intimately intermixed condition in the admixture and remove heat generated by the exothermic polymerization reaction.
- U.S. Pat. No. 7,037,999 issued on May 2, 2006 and entitled “Mid-Range Vinylidene Content Polyisobutylene Polymer Product and Process for Producing the Same” (hereinafter the '999 patent) describes, inter alia, mid-range vinylidene content PIB polymer products and processes for making the same.
- at least about 90% of the PIB molecules present in the product are polyisobutylene isomers having either alpha or beta position double bonds.
- the alpha (or terminal) position double bond (vinylidene) isomer content of the product may range from 20% to 70% thereof, and the content of tetra-substituted internal double bonds is very low, preferably less than about 5% and ideally less than about 1-2%.
- the mid-range vinylidene content PIB polymer products are desirably prepared by a liquid phase polymerization process conducted in a loop reactor similar to the reactors described in the '913 patent at a temperature which desirably may be about 60° F. or higher using a BF 3 /methanol catalyst complex and a contact time of no more than about 4 minutes.
- U.S. Pat. No. 6,992,152 issued on Jan. 31, 2006 and entitled “Apparatus and Method for Controlling Olefin Polymerization process” (hereinafter the '152 patent) relates, inter alia, to methodology for controlling the operation of reactors such as those described in the '999 and '913 patents so as to achieve efficiencies in process operation and better uniformity of the product of the process.
- the '152 patent describes methodology for controlling the ratio of BF 3 to catalyst composition to thereby control the reactivity (terminal double bond content) of the product.
- such control is achieved by providing for introduction of a catalyst modifier separately from the introduction of the catalyst composition itself.
- U.S. Pat. No. 6,844,401 issued on Jan. 18, 2005 and entitled “Apparatus for Preparing Polyolefin Products and Methodology for Using the Same” (hereinafter the '401 patent) relates, inter alia, to procedures, etc. for improving the processes described above.
- the '401 patent describes an olefin reactor system that includes at least two separate reactor zones operating in parallel. Such multiple reactor system provides process efficiencies and advantages particularly in connection with conversion rates and polymer polydispersity.
- the '401 patent describes downstream systems for quenching the residual catalyst leaving with the crude product to quickly prevent further reaction, for removal of catalyst residues by washing, and for separation of the product from unreacted monomer, dimers, oligomers and other undesirable contaminants such as diluents and the like.
- polyisobutylene products may be manufactured by processes comprising liquid phase polymerization conducted in a loop reactor at a temperature ranging from 30 to 90° F.
- the preferred catalyst may be a BF 3 /methanol catalyst complex and the reactor residence time may usually be no more than about 4 minutes.
- One of the preferred products may be a relatively low molecular weight, mid-range (50-60%) alpha position (vinylidene) double bond content PIB polymer. At least about 90% of the PIB molecules present in the product are either alpha position (vinylidene) double bond or beta position double bond isomers.
- the other polyisobutylene isomers produced generally may comprise less than 10% and ideally less than 5% of the molecules.
- Table 1 set forth below shows possible isomer structures that might be found in low molecular weight polyisobutylene products. Other isomers may possibly be included in minor amounts and should not affect the overall reactivity of the PIB molecule.
- PIB products produced in accordance with the processes described in the '913, '999, '152 and '401 patents discussed above contain mainly Structures I and IV with the other isomers being present in only minor concentrations.
- Highly reactive (HR) polyisobutylene products may generally contain about 80-85 mole % of Structure I (alpha position double bond) and about 15-20 mole % of Structure IV (beta position double bond).
- Mid-range vinylidene content PIB polymer products which may sometimes be referred to as “enhanced” products, also are generally predominantly comprised of only Structures I and IV, but generally in a ratio of about 55-60 mole % of Structure I and about 35-40 mole % of Structure IV, respectively, with minor concentrations of the other oligomers.
- the invention described herein provides a polyisobutylene production process that includes subjecting a reaction admixture containing isobutylene, a diluent for the isobutylene and a catalyst composition to reaction conditions suitable for causing at least a portion of the isobutylene to undergo polymerization to form a polyisobutylene product including polyisobutylene molecules
- the reaction conditions are preferably such that at least a fraction of the polyisobutylene molecules thus produced have alpha position (vinylidene) double bonds and the polyisobutylene product has a number average molecular weight and a polydispersity index.
- the process of the invention further includes the manipulation of the concentration of the diluent in the admixture to thereby control any one or more of (a) the relative size of the portion of the isobutylene that is converted to polyisobutylene, (b) the number average molecular weight of the product, (c) the polydispersity index of the product and (d) the relative size of the fraction of the polyisobutylene molecules thus produced that possess alpha position double bonds.
- the diluent may preferably comprise isobutane and the catalyst composition may comprise a complex of BF 3 and a primary alcohol complexing agent.
- the complexing agent may be methanol.
- the reaction admixture may preferably be subjected to suitable reaction conditions in a reaction zone where the reaction admixture is maintained in an intimately intermixed condition.
- the zone may comprise a loop reactor reaction zone.
- the relative size of the portion of the isobutylene that is converted to polyisobutylene is a direct function of the diluent concentration
- the polydispersity index of the product is an indirect function of the diluent concentration
- the average molecular weight of the product is an indirect function of the diluent concentration
- the relative size of the fraction of the produced polyisobutylene molecules having alpha position double bonds is a direct function of the diluent concentration.
- the concentration of the diluent in the admixture may be increased to thereby increase the relative size of said fraction and/or said portion, the concentration of the diluent in the admixture may be increased to thereby decrease the polydispersity index of the product, and the concentration of the diluent in the admixture may be decreased to thereby increase the average molecular weight of the product.
- the concentration of the diluent in the admixture should be no more than about 50 weight % and preferably. the concentration of the diluent in the admixture should be no more than about 30 weight %, and ideally the concentration of the diluent in the admixture should be in the range of from about 8 to about 15 weight %.
- a process which may include the step of selecting a diluent concentration for the admixture corresponding to a given relative size of said fraction, and the manipulating step may comprise maintaining the diluent content of the admixture at the selected concentration to thereby hold the relative size of said fraction essentially constant.
- the process may include the step of selecting a diluent concentration for the admixture corresponding to a given polydispersity index level, and the manipulating step may comprise maintaining the diluent content of the admixture at the selected concentration to thereby hold the polydispersity index of the product essentially constant.
- the process may include the step of selecting a diluent concentration for the admixture corresponding to a given relative size of said portion, and the manipulating step may comprise maintaining the diluent content of the admixture at the selected concentration to thereby hold the relative size of the portion essentially constant.
- the specific numerical correspondence between diluent concentration and any one or more of polydispersity index, molecular weight, size of fraction and/or size of portion will often need to be determined empirically in advance in order to have a set of values from which to select a predetermined diluent concentration.
- the content and/or characteristics of the product stream may simply be monitored and the diluent concentration varied as needed in response.
- the process may include the steps of treating the product to remove diluent and unreacted isobutylene therefrom and recycling at least one of the diluent and the unreacted isobutylene back to the reaction zone.
- the invention provides a process for production of polyisobutylene that comprises subjecting a reaction admixture comprising isobutylene, a diluent for the isobutylene and a catalyst composition to reaction conditions suitable for causing at least a portion of the isobutylene to undergo polymerization to form a polyisobutylene product including polyisobutylene molecules and wherein at least a fraction of the polyisobutylene molecules have alpha position double bonds, said polyisobutylene product having a number average molecular weight and a polydispersity index, said polyisobutylene product having at least one parameter that is variable as a function of the concentration of the diluent in the admixture, said at least one parameter comprising (a) the relative size of said fraction, (b) the number average molecular weight of the product, (c) the polydispersity index of the product or (d) the relative size of the portion.
- the process may include the steps of choosing a diluent concentration corresponding to a pre-selected value of said at least one parameter and then maintaining the admixture at said chosen diluent concentration to thereby hold said parameter at the pre-selected value.
- the parameter may comprises the relative size of said portion, the average molecular weight of the product, the polydispersity index of the product and/or the relative size of said fraction.
- the invention further provides an improved process for production of polyisobutylene wherein a reaction admixture including isobutylene, a diluent for the isobutylene and a catalyst composition is subjected to reaction conditions suitable for causing at least a portion of the isobutylene to undergo polymerization to form a polyisobutylene product including polyisobutylene molecules, wherein at least a fraction of the polyisobutylene molecules have alpha position double bonds and wherein the polyisobutylene product has a number average molecular weight and a polydispersity index, the improvement comprising increasing the concentration of the diluent in the admixture to thereby increase the relative size of said fraction, increase the relative size of said portion, decrease the number average molecular weight of the product, and/or decrease the polydispersity index of the product.
- the invention provides an improved process for production of polyisobutylene wherein a reaction admixture including isobutylene, a diluent for the isobutylene and a catalyst composition is subjected to reaction conditions suitable for causing at least a portion of the isobutylene to undergo polymerization to form a polyisobutylene product including polyisobutylene molecules, wherein at least a fraction of the polyisobutylene molecules have alpha position double bonds and wherein the polyisobutylene product has a number average molecular weight and a polydispersity index, the improvement comprising decreasing the concentration of the diluent in the admixture to thereby decrease the relative size of said fraction, decrease the relative size of said portion, increase the number average molecular weight of the product, and/or increase the polydispersity index of the product.
- the invention further provides novel polyisobutylene products produced by the processes described above.
- FIG. 1 is a schematic diagram illustrating a laboratory reactor arrangement set-up for conducting isobutylene polymerization processes in accordance with the invention
- FIG. 2 is a graph showing the variation of polymer alpha (vinylidene) double bond content with changing diluent concentration (data at 40° F.);
- FIG. 3 is a graph showing molecular weight (M N ) and polydispersity index (PDI) trends with changing diluent concentration (data at 40° F.) (filled symbols show M N values—left axis; unfilled symbols show PDI—right axis);
- FIG. 4 is a graph showing conversion trends with changing diluent content
- FIG. 5 is a schematic diagram depicting a PIB production process equipped for continuous recycling of isobutylene and/or diluent
- FIG. 6 is a graph showing variations in M N with changing diluent (isobutane) concentration
- FIG. 7 is a graph showing variations of viscosity (v) with changing diluent (isobutane) concentration
- FIG. 8 is a graph showing variations of PDI with changing diluent (isobutane) concentration.
- FIG. 9 is a graph showing variations of alpha (vinylidene) double bond content with changing diluent (isobutane) concentration.
- the concepts and principles of the invention described herein are generally applicable in connection with each of the various PIB reactors and PIB production processes illustrated in the '913, '999, '152 and '401 patents discussed above, and should be applicable in connection with all reactors and reactor systems that are used for the production of highly reactive and/or mid-range vinylidene content PIB polymer products using liquid phase polymerization procedures.
- the feedstock for such reactors may comprise either isobutylene or an admixture of isobutylene and a suitable non-reactive diluent (solvent) therefor.
- Suitable feedstocks are described generally in the '913, '999, '152 and '401 patents discussed above.
- a particularly preferred feedstock comprises a high purity isobutylene monomer having a composition as set forth below in Table 2.
- the diluent content in the reaction admixture may be 50 weight % or less, may desirably be 30 weight % or less, and may optimally be 10 weight % or less.
- the desired diluent for isobutylene may be isobutane,
- the desirable diluent should simply be capable of dissolving both isobutylene and polyisobutylene and should be inert to the polymer forming reactions taking place in the reactor.
- a C 3 - C 16 alkane or alkene, or a mixture of such substances may be used as the diluent.
- the diluent may be a C 3 - C 16 1-alkene such as, for example, butene-1.
- the diluent may advantageously comprise a mixture of hydrocarbons such as, for example, C 4 s and other light hydrocarbons.
- the processes of the present invention may generally and suitably be used in connection with the equipment and processes described in the '913, '999, '152 and '401 patents. However, for further clarity, the invention will be described here in connection with a simplified experimental reaction system 10 shown schematically in FIG. 1 .
- the experimental reaction system 10 may desirably include a loop reactor 10 , a recirculation pump 12 , an isobutylene monomer inlet 14 which may include a pump 16 , a diluent inlet 18 which also may include a diluent pump 20 , an inlet 22 for the catalyst complex (initiator), and chilling system 24 to remove the heat of the exothermic polymerization reaction.
- the loop reactor 10 may include segments 10 a, 10 b and 10 c as well as a pipe 26 which interconnects segments 10 a and 10 c as shown and provides a place for connection of pump 12 . And as can be seen in FIG.
- a chilling system 24 for the system may desirably include cooling jackets 24 a, 24 b and 24 c respectively for the reactor segments 10 a, 10 b and 10 c, a chilling fluid inlet 28 and a chilling fluid outlet 30 .
- the system may also include a feedstock inlet 32 , where the isobutylene monomer and a diluent are received and admixed for introduction into the reactor, and a product outlet 34 where the crude polymer product is withdrawn from the system.
- a reaction mixture comprising isobutylene, a diluent for the isobutylene and a catalyst composition are recirculated by pump 12 through reactor segments 10 a, 10 b and 10 c and pipe 26 while reaction conditions suitable for causing at least a portion of the isobutylene to undergo polymerization to form a polyisobutylene product including polyisobutylene molecules are maintained in the reactor 10 .
- isobutylene and a diluent therefor are introduced into the reactor 10 via inlet 32
- catalyst composition initiator
- crude product is withdrawn from the system via outlet 34 .
- the chain end concentrations of the isomers were measured using 13 C NMR spectroscopy.
- the molecular weight measurements were made using size exclusion chromatography (SEC).
- FIG. 2 shows variations in alpha position double bond isobutylene isomer content with changes in isobutane diluent concentration at 40° F.
- alpha isomer content increases with increased diluent concentration.
- the alpha isomer content of the product may be increased simply by increasing the concentration of the diluent in the reaction admixture.
- the alpha isomer content of the product may be decreased simply by decreasing the concentration of the diluent in the reaction admixture.
- M N number average molecular weight
- PDI polydispersity index
- the PDI of the product may be increased simply by decreasing the concentration of the diluent in the reaction admixture.
- the molecular weight of the product may be decreased simply by increasing the concentration of the diluent in the reaction admixture.
- the molecular weight of the product may be increased simply by decreasing the concentration of the diluent in the reaction admixture.
- the process also may provide for the continuous recycle of diluent and/or unreacted isobutylene.
- a reaction admixture comprising isobutylene, a diluent for isobutylene (advantageously isobutane) and a catalyst composition (preferably a complex of BF 3 and a complexing agent such as methanol) is subjected in reactor 200 to reaction conditions suitable for causing at least a portion of the isobutylene to undergo polymerization to form a polyisobutylene product including polyisobutylene molecules.
- the conditions in reactor 200 are such that at least a fraction of the thus produced polyisobutylene molecules in the product have alpha position double bonds and the polyisobutylene product has a number average molecular weight and a polydispersity index.
- the crude polyisobutylene product is washed in a scrubber 202 to remove catalyst residue and is subjected to flashing in a crude flash zone 204 to remove diluent and unreacted isobutylene.
- the product is then appropriately beneficiated further in a flash unit 212 and delivered downstream via outlet 24 .
- At least a portion of the diluent and unreacted isobutylene flashed in zone 204 may then desirably be continuously recycled overhead back to the reactor 200 via lines 206 and 208 .
- the diluent concentration in the reaction admixture in reactor 200 may desirably be manipulated and/or kept constant at any given time at such a level that it provides maximum benefit to the process in maintaining a desired alpha isomer content as well as in maintaining a low PDI. This, of course, may be done by adding diluent via line 216 .
- the feed rate of fresh isobutylene delivered via line 210 may then be determined by the isobutylene conversion rate in the reactor, i.e., the higher the conversion rate, the higher the rate of fresh isobutylene feed.
- the diluent concentration may be varied to alter the alpha isomer content of the product, the PDI of the product, the molecular weight of the product and/or the conversion rate. In this latter connection, it is noteworthy that the alpha isomer content of the product and the conversion rate vary directly with diluent concentration while product molecular weight and PDI vary indirectly with diluent concentration.
- reaction temperature of about 27° F. was maintained employing a chiller temperature of about 50° F.
- the input flow rate (isobutylene+diluent) was approximately 26 gpm and the volumetric flow rate of the recirculation pump was about 1260 gpm.
- the catalyst flow rate was adjusted (ideally to between 0.03 and 0.05 weight % of the feed rate) such that a constant operating temperature was maintained.
- the modifier was introduced separately into the reactor maintaining a methanol to catalyst ratio of 0.63:1 to synthesize a highly reactive (high vinylidene content) PIB product.
- M N molecular weight
- the PDI and the viscosity are within certain limits, usually dictated by product specifications.
- One such product may have the following specifications: M N —2100 to 2500; PDI—1.6 to 2.2; Kinematic Viscosity (v)—1500 to 1750; and Alpha double bond content—Greater than 80 mole %.
- the usual aim of the manufacturing process is that all these specifications be met simultaneously.
- the Kinematic viscosity (v) was measured using Cannon Fenske tubes immersed in a viscosity bath (Koehler KV3000).
- the M N and PDI measurements were obtained using SEC measurements as described earlier.
- the values obtained for the different parameters are as shown in FIG. 6 thru 9 .
- the dark heavy lines on the graphs show the desired specification parameters.
- An essentially pure isobutane stream having a composition as set forth in Table 5 below was obtained from ISGAS for use in an effort to isolate the effects on PIB production of minor impurities in the isobutane diluent, although in a real practical sense it is generally not feasible to use such a material in a commercial operation.
- the total oxygenate content of the pure diluent stream was less than about 5 ppm ( ⁇ 3,4 ppm methanol; ⁇ 1.4 ppm MTBE).
- the present invention provides a mechanism for greatly reducing both PDI and viscosity by increasing diluent concentration with no substantial corresponding decrease in molecular weight.
- both viscosity and PDI can be maintained within specifications while achieving a target molecular weight. This is especially important in the production of HR (high vinylidene) grades of PIB where controlling the polydispersity and viscosity within specifications is of paramount importance.
- HR high vinylidene
- the use of a lower purity isobutane diluent resulted in higher alpha double bond content as compared to high purity isobutane diluent.
- the invention provides the greatest benefit when the PIB production process is operated using a diluent concentration in the range of from about 8 to about 15 weight %, beyond which the gains are diminished as M N starts to decrease, especially when a lower purity (industrial grade) isobutane diluent is employed.
- alpha position double bond content increases with increasing isobutane dilution (in the impure isobutane example)
- the more desired manner to control alpha content by setting a suitable methanol to catalyst ratio. This is due to the fact that there usually is minimal control in an industrial setting over feedstock composition.
Abstract
Description
- None
- 1. Field of the Invention
- The invention described hereinafter relates to improvements in the polymerization of isobutylene. In particular the invention relates to processes for preparing polyisobutylene (PIB) products having improved characteristics. More particularly, the invention relates to techniques for manipulation and control of liquid phase processes for producing polyisobutylene, polyisobutylene products having pre-selected characteristics, and methodology which enhances the operation and control of polyisobutylene reactors.
- 2. Background of the Invention
- U.S. Pat. No. 6,562,913 issued on May 13, 2003 and entitled “Process for Producing High Vinylidene Polyisobutylene” (hereinafter the '913 patent) relates, inter alia, to liquid phase polymerization processes for preparing low molecular weight (number average molecular weight (MN) less than about 10,000), highly reactive (terminal double bond content of at least about 70%) polyisobutylene products. In accordance with the disclosure of the '913 patent, a catalyst composition, which desirably may comprise a complex of BF3 and complexing agent such as methanol, and a feedstock containing isobutylene, are each introduced into a reaction zone where the same are intimately admixed with residual reaction mixture so as to present an intimately intermixed reaction admixture in the reaction zone. The intimately intermixed reaction admixture is maintained in its intimately intermixed condition and at a relatively constant temperature of at least about 0° C. while the same is in the reaction zone, whereby isobutylene therein is polymerized to form a polyisobutylene product having a high degree of terminal (vinylidene) unsaturation. A crude product stream comprising residual catalyst composition, unreacted isobutylene and polyisobutylene is then withdrawn from the reaction zone. The introduction of feedstock into and the withdrawal of product stream from the reaction zone are each controlled such that the residence time of the isobutylene undergoing polymerization in the reaction zone is no greater than about 4 minutes, whereby the product stream contains a highly reactive polyisobutylene product. Preferably, the reaction zone may be the tube side of a shell-and-tube exchanger in which a coolant is circulated on the shell side. A recirculation loop may desirably be employed to circulate the reaction admixture through the tube side reaction zone at a linear velocity sufficient to establish and maintain an intimately intermixed condition in the admixture and remove heat generated by the exothermic polymerization reaction.
- U.S. Pat. No. 7,037,999 issued on May 2, 2006 and entitled “Mid-Range Vinylidene Content Polyisobutylene Polymer Product and Process for Producing the Same” (hereinafter the '999 patent) describes, inter alia, mid-range vinylidene content PIB polymer products and processes for making the same. In accordance with the disclosure of the '999 patent, at least about 90% of the PIB molecules present in the product are polyisobutylene isomers having either alpha or beta position double bonds. The alpha (or terminal) position double bond (vinylidene) isomer content of the product may range from 20% to 70% thereof, and the content of tetra-substituted internal double bonds is very low, preferably less than about 5% and ideally less than about 1-2%. The mid-range vinylidene content PIB polymer products are desirably prepared by a liquid phase polymerization process conducted in a loop reactor similar to the reactors described in the '913 patent at a temperature which desirably may be about 60° F. or higher using a BF3/methanol catalyst complex and a contact time of no more than about 4 minutes.
- U.S. Pat. No. 6,992,152 issued on Jan. 31, 2006 and entitled “Apparatus and Method for Controlling Olefin Polymerization process” (hereinafter the '152 patent) relates, inter alia, to methodology for controlling the operation of reactors such as those described in the '999 and '913 patents so as to achieve efficiencies in process operation and better uniformity of the product of the process. In particular, the '152 patent describes methodology for controlling the ratio of BF3 to catalyst composition to thereby control the reactivity (terminal double bond content) of the product. Specifically, such control is achieved by providing for introduction of a catalyst modifier separately from the introduction of the catalyst composition itself.
- U.S. Pat. No. 6,844,401 issued on Jan. 18, 2005 and entitled “Apparatus for Preparing Polyolefin Products and Methodology for Using the Same” (hereinafter the '401 patent) relates, inter alia, to procedures, etc. for improving the processes described above. In particular the '401 patent describes an olefin reactor system that includes at least two separate reactor zones operating in parallel. Such multiple reactor system provides process efficiencies and advantages particularly in connection with conversion rates and polymer polydispersity. In addition, the '401 patent describes downstream systems for quenching the residual catalyst leaving with the crude product to quickly prevent further reaction, for removal of catalyst residues by washing, and for separation of the product from unreacted monomer, dimers, oligomers and other undesirable contaminants such as diluents and the like.
- In accordance with certain of the preferred embodiments of the '913, '999, '152 and '401 patents, polyisobutylene products may be manufactured by processes comprising liquid phase polymerization conducted in a loop reactor at a temperature ranging from 30 to 90° F. The preferred catalyst may be a BF3/methanol catalyst complex and the reactor residence time may usually be no more than about 4 minutes. One of the preferred products may be a relatively low molecular weight, mid-range (50-60%) alpha position (vinylidene) double bond content PIB polymer. At least about 90% of the PIB molecules present in the product are either alpha position (vinylidene) double bond or beta position double bond isomers. The other polyisobutylene isomers produced generally may comprise less than 10% and ideally less than 5% of the molecules.
- Table 1 set forth below shows possible isomer structures that might be found in low molecular weight polyisobutylene products. Other isomers may possibly be included in minor amounts and should not affect the overall reactivity of the PIB molecule.
- In general, the reactivity of an olefinic double bond is directly related to its degree of substitution. That is to say, the more highly substituted the olefinic double bond, the less reactive it is. Therefore, since Structure I (alpha position or vinylidene double bond) of Table 1 is only disubstituted, it is much more reactive than Structures II, III or IV where the double bond is in a beta position. Structures II and III are both 1,2,2 trisubstituted and are less reactive than Structure I, but because there is an available hydrogen on the terminal carbon, they are more reactive than Structure IV which is 1,1,2-trisubstituted with no terminal hydrogen. Structure V is tetra-substituted and is the least reactive of all the depicted isomers.
- Generally speaking, PIB products produced in accordance with the processes described in the '913, '999, '152 and '401 patents discussed above contain mainly Structures I and IV with the other isomers being present in only minor concentrations. Highly reactive (HR) polyisobutylene products (see the '913 patent) may generally contain about 80-85 mole % of Structure I (alpha position double bond) and about 15-20 mole % of Structure IV (beta position double bond). Mid-range vinylidene content PIB polymer products (see the '999 patent), which may sometimes be referred to as “enhanced” products, also are generally predominantly comprised of only Structures I and IV, but generally in a ratio of about 55-60 mole % of Structure I and about 35-40 mole % of Structure IV, respectively, with minor concentrations of the other oligomers.
- The '913, '999, '152 and '401 patents discussed above are each assigned to the assignee of the present application, and the entireties of the respective disclosures thereof are specifically incorporated herein by this reference thereto.
- In conducting the processes described above, highly specialized equipment and procedures may often be utilized to enhance the operation and control of the polymerization reactions that are involved. Moreover, as in any industrial activity, methodology and/or equipment for enhancing capacity and throughput are sought continually. In particular it is often very important in production of polyisobutylene to be able to carefully control (optimize) the rate at which the isobutylene is converted to polyisobutylene (conversion rate). It is also highly important in many cases to be able to carefully control (optimize) the polydispersity index (PDI) and/or the number average molecular weight (MN) of the polyisobutylene product. Even more importantly, it is extremely valuable in many commercial applications to be able to carefully control the concentration of reactive (terminal) double bonds in the polyisobutylene product.
- In accordance with the concepts and principles of the invention described herein, a process for production of polyisobutylene is provided which addresses the issues presented in connection with prior art processes such as those described above. In particular, in one of its several important aspects, the invention described herein provides a polyisobutylene production process that includes subjecting a reaction admixture containing isobutylene, a diluent for the isobutylene and a catalyst composition to reaction conditions suitable for causing at least a portion of the isobutylene to undergo polymerization to form a polyisobutylene product including polyisobutylene molecules The reaction conditions are preferably such that at least a fraction of the polyisobutylene molecules thus produced have alpha position (vinylidene) double bonds and the polyisobutylene product has a number average molecular weight and a polydispersity index. The process of the invention further includes the manipulation of the concentration of the diluent in the admixture to thereby control any one or more of (a) the relative size of the portion of the isobutylene that is converted to polyisobutylene, (b) the number average molecular weight of the product, (c) the polydispersity index of the product and (d) the relative size of the fraction of the polyisobutylene molecules thus produced that possess alpha position double bonds.
- In further accordance with the concepts and principles of the invention, the diluent may preferably comprise isobutane and the catalyst composition may comprise a complex of BF3 and a primary alcohol complexing agent. Ideally, the complexing agent may be methanol.
- In further accordance with the invention, the reaction admixture may preferably be subjected to suitable reaction conditions in a reaction zone where the reaction admixture is maintained in an intimately intermixed condition. Ideally, the zone may comprise a loop reactor reaction zone.
- In still further accordance with the concepts and principles of the invention, it has been found that the relative size of the portion of the isobutylene that is converted to polyisobutylene is a direct function of the diluent concentration, the polydispersity index of the product is an indirect function of the diluent concentration, the average molecular weight of the product is an indirect function of the diluent concentration, and the relative size of the fraction of the produced polyisobutylene molecules having alpha position double bonds is a direct function of the diluent concentration. Thus, and again in accordance with the concepts and principles of the invention, the concentration of the diluent in the admixture may be increased to thereby increase the relative size of said fraction and/or said portion, the concentration of the diluent in the admixture may be increased to thereby decrease the polydispersity index of the product, and the concentration of the diluent in the admixture may be decreased to thereby increase the average molecular weight of the product.
- Desirably, the concentration of the diluent in the admixture should be no more than about 50 weight % and preferably. the concentration of the diluent in the admixture should be no more than about 30 weight %, and ideally the concentration of the diluent in the admixture should be in the range of from about 8 to about 15 weight %.
- In further accord with the concepts and principles of the invention, a process is provided which may include the step of selecting a diluent concentration for the admixture corresponding to a given relative size of said fraction, and the manipulating step may comprise maintaining the diluent content of the admixture at the selected concentration to thereby hold the relative size of said fraction essentially constant. In addition the process may include the step of selecting a diluent concentration for the admixture corresponding to a given polydispersity index level, and the manipulating step may comprise maintaining the diluent content of the admixture at the selected concentration to thereby hold the polydispersity index of the product essentially constant. Also, the process may include the step of selecting a diluent concentration for the admixture corresponding to a given relative size of said portion, and the manipulating step may comprise maintaining the diluent content of the admixture at the selected concentration to thereby hold the relative size of the portion essentially constant. Of course, as would be readily understood by the routineer in the olefin polymerization art, the specific numerical correspondence between diluent concentration and any one or more of polydispersity index, molecular weight, size of fraction and/or size of portion will often need to be determined empirically in advance in order to have a set of values from which to select a predetermined diluent concentration. Conversely, the content and/or characteristics of the product stream may simply be monitored and the diluent concentration varied as needed in response.
- In further accordance with the invention, the process may include the steps of treating the product to remove diluent and unreacted isobutylene therefrom and recycling at least one of the diluent and the unreacted isobutylene back to the reaction zone.
- Furthermore, the invention provides a process for production of polyisobutylene that comprises subjecting a reaction admixture comprising isobutylene, a diluent for the isobutylene and a catalyst composition to reaction conditions suitable for causing at least a portion of the isobutylene to undergo polymerization to form a polyisobutylene product including polyisobutylene molecules and wherein at least a fraction of the polyisobutylene molecules have alpha position double bonds, said polyisobutylene product having a number average molecular weight and a polydispersity index, said polyisobutylene product having at least one parameter that is variable as a function of the concentration of the diluent in the admixture, said at least one parameter comprising (a) the relative size of said fraction, (b) the number average molecular weight of the product, (c) the polydispersity index of the product or (d) the relative size of the portion. In accordance with this aspect of the invention, the process may include the steps of choosing a diluent concentration corresponding to a pre-selected value of said at least one parameter and then maintaining the admixture at said chosen diluent concentration to thereby hold said parameter at the pre-selected value. In further accordance with this aspect of the invention, the parameter may comprises the relative size of said portion, the average molecular weight of the product, the polydispersity index of the product and/or the relative size of said fraction.
- The invention further provides an improved process for production of polyisobutylene wherein a reaction admixture including isobutylene, a diluent for the isobutylene and a catalyst composition is subjected to reaction conditions suitable for causing at least a portion of the isobutylene to undergo polymerization to form a polyisobutylene product including polyisobutylene molecules, wherein at least a fraction of the polyisobutylene molecules have alpha position double bonds and wherein the polyisobutylene product has a number average molecular weight and a polydispersity index, the improvement comprising increasing the concentration of the diluent in the admixture to thereby increase the relative size of said fraction, increase the relative size of said portion, decrease the number average molecular weight of the product, and/or decrease the polydispersity index of the product.
- Conversely the invention provides an improved process for production of polyisobutylene wherein a reaction admixture including isobutylene, a diluent for the isobutylene and a catalyst composition is subjected to reaction conditions suitable for causing at least a portion of the isobutylene to undergo polymerization to form a polyisobutylene product including polyisobutylene molecules, wherein at least a fraction of the polyisobutylene molecules have alpha position double bonds and wherein the polyisobutylene product has a number average molecular weight and a polydispersity index, the improvement comprising decreasing the concentration of the diluent in the admixture to thereby decrease the relative size of said fraction, decrease the relative size of said portion, increase the number average molecular weight of the product, and/or increase the polydispersity index of the product.
- The invention further provides novel polyisobutylene products produced by the processes described above.
-
FIG. 1 is a schematic diagram illustrating a laboratory reactor arrangement set-up for conducting isobutylene polymerization processes in accordance with the invention; -
FIG. 2 is a graph showing the variation of polymer alpha (vinylidene) double bond content with changing diluent concentration (data at 40° F.); -
FIG. 3 is a graph showing molecular weight (MN) and polydispersity index (PDI) trends with changing diluent concentration (data at 40° F.) (filled symbols show MN values—left axis; unfilled symbols show PDI—right axis); -
FIG. 4 is a graph showing conversion trends with changing diluent content; -
FIG. 5 is a schematic diagram depicting a PIB production process equipped for continuous recycling of isobutylene and/or diluent; -
FIG. 6 is a graph showing variations in MN with changing diluent (isobutane) concentration; -
FIG. 7 is a graph showing variations of viscosity (v) with changing diluent (isobutane) concentration; -
FIG. 8 is a graph showing variations of PDI with changing diluent (isobutane) concentration; and -
FIG. 9 is a graph showing variations of alpha (vinylidene) double bond content with changing diluent (isobutane) concentration. - The concepts and principles of the invention described herein are generally applicable in connection with each of the various PIB reactors and PIB production processes illustrated in the '913, '999, '152 and '401 patents discussed above, and should be applicable in connection with all reactors and reactor systems that are used for the production of highly reactive and/or mid-range vinylidene content PIB polymer products using liquid phase polymerization procedures. In this regard, it is to be noted that the feedstock for such reactors may comprise either isobutylene or an admixture of isobutylene and a suitable non-reactive diluent (solvent) therefor. Suitable feedstocks are described generally in the '913, '999, '152 and '401 patents discussed above. A particularly preferred feedstock comprises a high purity isobutylene monomer having a composition as set forth below in Table 2.
-
TABLE 2 Concentrations of individual components of Isobutylene stream Component Weight % Methane 0.026 Ethane 0.0006 Propane 0.0024 Propylene 0.027 Isobutane 0.064 N-butane 0.010 Butene-1 0.016 Isobutylene 99.84 T-butene-2 0.010 C-butene-2 0.063 1,3 butadiene 0.007 C5+ 0.007 - In accordance with the concepts and principles of the invention, in the liquid phase production of polyisobutylene, an important and formerly unknown relationship between diluent concentration and the alpha vinylidene content of the product has been discovered. That is to say, in accordance with the concepts and principles of the invention, it has been discovered that an increase in diluent concentration in the reaction admixture generally results in higher alpha position (vinylidene) double bonds concentration in the product. Moreover, in the same manner, an increase in diluent concentration leads generally to greatly improved (narrower) polydispersity indices. In these regards, and in further accordance with the invention, the diluent content in the reaction admixture may be 50 weight % or less, may desirably be 30 weight % or less, and may optimally be 10 weight % or less. Ideally the desired diluent for isobutylene may be isobutane, However, in a more general sense, the desirable diluent should simply be capable of dissolving both isobutylene and polyisobutylene and should be inert to the polymer forming reactions taking place in the reactor. In this latter regard, a C3- C16 alkane or alkene, or a mixture of such substances, may be used as the diluent. Desirably the diluent may be a C3- C16 1-alkene such as, for example, butene-1. In another sense, the diluent may advantageously comprise a mixture of hydrocarbons such as, for example, C4s and other light hydrocarbons.
- As mentioned above, the processes of the present invention may generally and suitably be used in connection with the equipment and processes described in the '913, '999, '152 and '401 patents. However, for further clarity, the invention will be described here in connection with a simplified
experimental reaction system 10 shown schematically inFIG. 1 . - With reference to
FIG. 1 , theexperimental reaction system 10 may desirably include aloop reactor 10, arecirculation pump 12, anisobutylene monomer inlet 14 which may include apump 16, adiluent inlet 18 which also may include adiluent pump 20, aninlet 22 for the catalyst complex (initiator), and chillingsystem 24 to remove the heat of the exothermic polymerization reaction. As shown, theloop reactor 10 may includesegments 10 a, 10 b and 10 c as well as apipe 26 which interconnectssegments 10 a and 10 c as shown and provides a place for connection ofpump 12. And as can be seen inFIG. 1 , achilling system 24 for the system may desirably include coolingjackets reactor segments 10 a, 10 b and 10 c, achilling fluid inlet 28 and achilling fluid outlet 30. In addition, the system may also include afeedstock inlet 32, where the isobutylene monomer and a diluent are received and admixed for introduction into the reactor, and aproduct outlet 34 where the crude polymer product is withdrawn from the system. - In operation, a reaction mixture comprising isobutylene, a diluent for the isobutylene and a catalyst composition are recirculated by
pump 12 throughreactor segments 10 a, 10 b and 10 c andpipe 26 while reaction conditions suitable for causing at least a portion of the isobutylene to undergo polymerization to form a polyisobutylene product including polyisobutylene molecules are maintained in thereactor 10. In the meanwhile, isobutylene and a diluent therefor are introduced into thereactor 10 viainlet 32, catalyst composition (initiator) is introduced into the reactor viainlet 22 and crude product is withdrawn from the system viaoutlet 34. - Using the
system 10, experiments were conducted maintaining the total flow rate of monomer to the reactor loop at 100 mL/min. Reactions were carried out at temperatures of 40° F. and 60° F. The pressure in the reactor loop was maintained at 200 psi. The internal diameter of the reactor tubes was 0.305″ and the total reactor volume was 228 cm3. Catalyst (initiator) flow was controlled at 0.02 mL/min such that the reaction set point was maintained. The recirculation rate in the reactor loop was 2 gpm. The catalyst composition comprised a complex of BF3 and methanol wherein the molar ratio of BF3 to methanol was 1:1. No modifier (methanol) was added to the reactor separately from the catalyst complex, although such a step might be desirable under some conditions. In this latter regard, the separate addition of modifier is described in detail in the '152 patent discussed above. A high purity isobutylene (purity>99.5 weight %) was used as the feedstock and a relatively high purity isobutane (purity 95 to 98 weight %) was used as the diluent. - Experiments were conducted at various diluent concentration levels to study the effect of diluent concentration on alpha position double bond content, molecular weight (MN) and polydispersity index (PDI) of the product. In these experiments, the diluent level was varied between 0 and 27 weight %.
- The chain end concentrations of the isomers were measured using 13C NMR spectroscopy. The molecular weight measurements were made using size exclusion chromatography (SEC).
- The results of the experimentation are illustrated in
FIGS. 2 , 3 and 4.FIG. 2 shows variations in alpha position double bond isobutylene isomer content with changes in isobutane diluent concentration at 40° F. And as can be seen inFIG. 2 , alpha isomer content increases with increased diluent concentration. Thus it is clear that the alpha isomer content of the product may be increased simply by increasing the concentration of the diluent in the reaction admixture. Also it is clear that if other conditions dictate, the alpha isomer content of the product may be decreased simply by decreasing the concentration of the diluent in the reaction admixture. - With reference to
FIG. 3 , the influence of diluent concentration on number average molecular weight (MN) and polydispersity index (PDI) can be seen. InFIG. 3 , MN values are shown on the left axis and are represented by the filled symbols, while PDI values are shown on the right axis and are represented by the unfilled symbols. Of particular interest is the large drop in PDI at almost constant molecular weight between 0 and 10 wt % of diluent (isobutane) concentration. This may be of particular benefit in meeting the commercially valuable polydispersity specifications for PIB polymers. Thus it is clear that the PDI of the product may be decreased simply by increasing the concentration of the diluent in the reaction admixture. Also it is clear that if other conditions dictate, the PDI of the product may be increased simply by decreasing the concentration of the diluent in the reaction admixture. Furthermore it is clear that the molecular weight of the product may be decreased simply by increasing the concentration of the diluent in the reaction admixture. Also it is clear that if other conditions dictate, the molecular weight of the product may be increased simply by decreasing the concentration of the diluent in the reaction admixture. - With reference to
FIG. 4 it can also be seen that the rate of conversion of isobutylene into polyisobutylene increases with increasing diluent content. This perhaps can be attributed to the fact that higher diluent concentrations in the reactor may provide improved heat transfer characteristics. - As can be seen from the foregoing, alpha isomer content increases, polydispersity decreases, conversion increases and molecular weight decreases with increasing isobutane diluent concentration. Trends similar to those observed at 40° F. were also observed when the polymerization reactions were conducted at 60° F. Tabulated experimental data is reported below in Tables 3 and 4. As can be seen, these Tables also show the concentration of alpha and beta isomers in the polyisobutylene product obtained.
-
TABLE 3 Data showing the effect of diluent concentration on PIB properties at 40° F. Number Isobutane Average Concentration Concentration Diluent Molecular of Alpha of Beta Concentration Weight Polydispersity Isomer Isomer Other Conversion (wt %) (MN) Index (PDI) (Structure I) (Structure IV) Isomers Rate 0 3318 3.81 54.2 NA NA 17.9 5 3288 3.31 56.5 33.6 9.9 22.1 10 3155 2.47 59.9 32.3 7.8 24.6 15 2909 2.25 65.4 32.5 2.1 27.2 20 2724 2.22 73.41 18.1 8.4 29.1 27 1785 2.19 75.3 20.3 4.4 33.4 -
TABLE 4 Data showing the effect of diluent concentration on PIB properties at 60° F. Number Isobutane Average Concentration Diluent Molecular of Alpha Concentration Concentration Weight Polydispersity Isomer of Beta Isomer Other Conversion (wt %) (MN) Index (PDI) (Structure I) (Structure IV) Isomers Rate 0 2249 2.71 53.0 NA NA 48.3 5 2373 2.23 54.4 34.8 10.8 52.3 10 2217 2.17 63.1 30.7 6.2 51.5 15 1637 1.91 69.5 25.3 5.2 57.5 20 1389 1.89 70.0 22.9 7.1 57.7 27 1109 1.85 73.3 17.6 9.1 62.3 - In further accordance with the concepts and principles of the invention, the process also may provide for the continuous recycle of diluent and/or unreacted isobutylene. Such a process is depicted schematically in
FIG. 5 . With reference toFIG. 5 , a reaction admixture comprising isobutylene, a diluent for isobutylene (advantageously isobutane) and a catalyst composition (preferably a complex of BF3 and a complexing agent such as methanol) is subjected inreactor 200 to reaction conditions suitable for causing at least a portion of the isobutylene to undergo polymerization to form a polyisobutylene product including polyisobutylene molecules. The conditions inreactor 200 are such that at least a fraction of the thus produced polyisobutylene molecules in the product have alpha position double bonds and the polyisobutylene product has a number average molecular weight and a polydispersity index. Upon leaving thereactor 200 the crude polyisobutylene product is washed in ascrubber 202 to remove catalyst residue and is subjected to flashing in acrude flash zone 204 to remove diluent and unreacted isobutylene. The product is then appropriately beneficiated further in aflash unit 212 and delivered downstream viaoutlet 24. At least a portion of the diluent and unreacted isobutylene flashed inzone 204 may then desirably be continuously recycled overhead back to thereactor 200 vialines 206 and 208. The diluent concentration in the reaction admixture inreactor 200 may desirably be manipulated and/or kept constant at any given time at such a level that it provides maximum benefit to the process in maintaining a desired alpha isomer content as well as in maintaining a low PDI. This, of course, may be done by adding diluent via line 216. The feed rate of fresh isobutylene delivered vialine 210 may then be determined by the isobutylene conversion rate in the reactor, i.e., the higher the conversion rate, the higher the rate of fresh isobutylene feed. In addition, whenever desired, the diluent concentration may be varied to alter the alpha isomer content of the product, the PDI of the product, the molecular weight of the product and/or the conversion rate. In this latter connection, it is noteworthy that the alpha isomer content of the product and the conversion rate vary directly with diluent concentration while product molecular weight and PDI vary indirectly with diluent concentration. - Additional experimental data was gathered in connection with studies involving the synthesis of a highly reactive grade (alpha double bond content more than 80%) PIB using a scaled up version of a reactor which is set up essentially the same as the
reactor 10. In connection with these studies, additional modifier is introduced essentially as described in the '152 patent. These studies reveal that it is greatly beneficial to operate the reactor using an isobutane diluent concentration of about 8-15 weight % and the following discussion is based on data derived therefrom. - In these studies a reaction temperature of about 27° F. was maintained employing a chiller temperature of about 50° F. The input flow rate (isobutylene+diluent) was approximately 26 gpm and the volumetric flow rate of the recirculation pump was about 1260 gpm.
- The catalyst flow rate was adjusted (ideally to between 0.03 and 0.05 weight % of the feed rate) such that a constant operating temperature was maintained. As per the '152 patent, the modifier was introduced separately into the reactor maintaining a methanol to catalyst ratio of 0.63:1 to synthesize a highly reactive (high vinylidene content) PIB product. In a highly reactive product, it is desirable for the molecular weight (MN), the PDI and the viscosity to be within certain limits, usually dictated by product specifications. One such product may have the following specifications: MN—2100 to 2500; PDI—1.6 to 2.2; Kinematic Viscosity (v)—1500 to 1750; and Alpha double bond content—Greater than 80 mole %. The usual aim of the manufacturing process is that all these specifications be met simultaneously.
- In connection with the foregoing, the Kinematic viscosity (v) was measured using Cannon Fenske tubes immersed in a viscosity bath (Koehler KV3000). The MN and PDI measurements were obtained using SEC measurements as described earlier. The values obtained for the different parameters are as shown in
FIG. 6 thru 9. The dark heavy lines on the graphs show the desired specification parameters. - An essentially pure isobutane stream having a composition as set forth in Table 5 below was obtained from ISGAS for use in an effort to isolate the effects on PIB production of minor impurities in the isobutane diluent, although in a real practical sense it is generally not feasible to use such a material in a commercial operation. The total oxygenate content of the pure diluent stream was less than about 5 ppm (≈3,4 ppm methanol; ≈1.4 ppm MTBE).
-
TABLE 5 Purity of individual components of Isobutane diluent (99.8% purity) Components Weight % Propane 0.02 Isobutane 99.79 N-butane 0.18 - The experimental set-up and conditions for these efforts were essentially the same as those described above in connection with
reaction system 10. The experimental data obtained as a result of these efforts are set forth below in Table 6. -
TABLE 6 Product properties obtained using high purity Isobutane Alpha position Isobutane double diluent bond concentration Kinematic content weight % MN PDI Viscosity mole % 0 3292 4 3489 61.4 8 3197.7 2.55 2693 58.5 13 2946.9 2.48 2637 59.9 18 2883 2.43 2628 60.1 25 2751 2.29 2213 60.3 - It can be observed from Table 6 that the major advantage of being able to operate so as to produce a PIB having decreased polydispersity was achieved. That is to say a substantial decrease in PDI and simultaneously in viscosity is achieved with increasing diluent concentration, while almost constant molecular weight is maintained. This is beneficial in a commercial sense for meeting both MN and PDI/viscosity specifications simultaneously. However, there is almost no change in the alpha double bond content with increasing isobutane diluent concentration as was observed in the case of lower purity isobutane.
- In view of the foregoing it is clear that the present invention provides a mechanism for greatly reducing both PDI and viscosity by increasing diluent concentration with no substantial corresponding decrease in molecular weight. In addition, both viscosity and PDI can be maintained within specifications while achieving a target molecular weight. This is especially important in the production of HR (high vinylidene) grades of PIB where controlling the polydispersity and viscosity within specifications is of paramount importance. Moreover, the use of a lower purity isobutane diluent resulted in higher alpha double bond content as compared to high purity isobutane diluent. This could be the result of the presence of other hydrocarbon components in the feed or could be due to the presence of oxygenates other than methanol. With regard to the foregoing, it seems to be more likely that the other oxygenates play a role in the increased vinylidene content. In accordance with our studies, the primary suspect is dimethyl ether. These oxygenates play a role similar to additional methanol that is added as a modifier. As is known, methanol is also an oxygenate which may be added in a controlled manner to regulate vinylidene content.
- It appears that the invention provides the greatest benefit when the PIB production process is operated using a diluent concentration in the range of from about 8 to about 15 weight %, beyond which the gains are diminished as MN starts to decrease, especially when a lower purity (industrial grade) isobutane diluent is employed.
- Although alpha position double bond content increases with increasing isobutane dilution (in the impure isobutane example), the more desired manner to control alpha content by setting a suitable methanol to catalyst ratio. This is due to the fact that there usually is minimal control in an industrial setting over feedstock composition.
Claims (54)
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/468,195 US20100298507A1 (en) | 2009-05-19 | 2009-05-19 | Polyisobutylene Production Process With Improved Efficiencies And/Or For Forming Products Having Improved Characteristics And Polyisobutylene Products Produced Thereby |
CN2010800323328A CN102803300A (en) | 2009-05-19 | 2010-04-05 | Polyisobutylene production process with improved efficiencies and/or for forming products having improved characteristics and polyisobutylene product produced thereby |
KR1020117030211A KR20120026552A (en) | 2009-05-19 | 2010-04-05 | Polyisobutylene production process with improved efficiencies and/or for forming products having improved characteristics and polyisobutylene product produced thereby |
EP10778074A EP2432806A4 (en) | 2009-05-19 | 2010-04-05 | Polyisobutylene production process with improved efficiencies and/or for forming products having improved characteristics and polyisobutylene product produced thereby |
PCT/US2010/029892 WO2010135034A1 (en) | 2009-05-19 | 2010-04-05 | Polyisobutylene production process with improved efficiencies and/or for forming products having improved characteristics and polyisobutylene product produced thereby |
TW099112005A TW201041903A (en) | 2009-05-19 | 2010-04-16 | Polyisobutylene production process with improved efficiencies and/or for forming products having improved characteristics and polyisobutylene products produced thereby |
SA110310388A SA110310388B1 (en) | 2009-05-19 | 2010-05-17 | Polyisobutylene production process with 1-alkene diluent |
US12/932,837 US9809665B2 (en) | 2009-05-19 | 2011-03-08 | Polyisobutylene production process with improved efficiencies and/or for forming products having improved characteristics and polyisobutylene products produced thereby |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/468,195 US20100298507A1 (en) | 2009-05-19 | 2009-05-19 | Polyisobutylene Production Process With Improved Efficiencies And/Or For Forming Products Having Improved Characteristics And Polyisobutylene Products Produced Thereby |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/932,837 Division US9809665B2 (en) | 2009-05-19 | 2011-03-08 | Polyisobutylene production process with improved efficiencies and/or for forming products having improved characteristics and polyisobutylene products produced thereby |
Publications (1)
Publication Number | Publication Date |
---|---|
US20100298507A1 true US20100298507A1 (en) | 2010-11-25 |
Family
ID=43124981
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/468,195 Abandoned US20100298507A1 (en) | 2009-05-19 | 2009-05-19 | Polyisobutylene Production Process With Improved Efficiencies And/Or For Forming Products Having Improved Characteristics And Polyisobutylene Products Produced Thereby |
US12/932,837 Active 2030-08-18 US9809665B2 (en) | 2009-05-19 | 2011-03-08 | Polyisobutylene production process with improved efficiencies and/or for forming products having improved characteristics and polyisobutylene products produced thereby |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/932,837 Active 2030-08-18 US9809665B2 (en) | 2009-05-19 | 2011-03-08 | Polyisobutylene production process with improved efficiencies and/or for forming products having improved characteristics and polyisobutylene products produced thereby |
Country Status (7)
Country | Link |
---|---|
US (2) | US20100298507A1 (en) |
EP (1) | EP2432806A4 (en) |
KR (1) | KR20120026552A (en) |
CN (1) | CN102803300A (en) |
SA (1) | SA110310388B1 (en) |
TW (1) | TW201041903A (en) |
WO (1) | WO2010135034A1 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012170411A2 (en) * | 2011-06-08 | 2012-12-13 | Tpc Group L.L.C. | Production of highly reactive low molecular weight pib oligomers |
WO2013062758A1 (en) * | 2011-10-26 | 2013-05-02 | Tpc Group Llc | Polyisobutylene prepared at high velocity and circulation rate |
WO2013062763A1 (en) * | 2011-10-26 | 2013-05-02 | Tpc Group Llc | Polyisobutylene prepared with low diluent content reaction medium |
WO2013062759A1 (en) * | 2011-10-26 | 2013-05-02 | Tpc Group Llc | Mid-range vinylidene content, high viscosity polyisobutylene polymers |
WO2013192186A1 (en) * | 2012-06-18 | 2013-12-27 | Petrochemical Supply, Inc. | Polyisobutylene composition having internal vinylidene and process for preparing the polyisobutylene polymer composition |
US20150322181A1 (en) * | 2013-01-17 | 2015-11-12 | Daelim Industrial Co., Ltd. | Method for preparing polybutene |
US9617366B1 (en) | 2016-03-03 | 2017-04-11 | Tpc Group Llc | Low-fluoride, reactive polyisobutylene |
US9617363B1 (en) | 2016-03-03 | 2017-04-11 | Tpc Group Llc | Low-fluoride, reactive polyisobutylene |
WO2017151341A1 (en) | 2016-03-03 | 2017-09-08 | Tpc Group Llc | Low-fluoride, reactive polyisobutylene |
WO2019075356A3 (en) * | 2017-10-14 | 2019-07-04 | Tpc Group Llc | Non-random isobutylene copolymers |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3022239B1 (en) * | 2013-07-17 | 2017-04-05 | Basf Se | Highly reactive polyisobutylene having a high percentage of vinylidene double bonds in the side chains |
CN103641939A (en) * | 2013-11-27 | 2014-03-19 | 河北科技大学 | Preparation system and preparation method for polyisobutylene |
Citations (89)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US132264A (en) * | 1872-10-15 | Improvement in treating ammoniacal liquors of gas-works,gc | ||
US2139038A (en) * | 1935-02-07 | 1938-12-06 | Standard Oil Dev Co | Process for producing polymers of olefines |
US2379656A (en) * | 1940-08-23 | 1945-07-03 | Robert F Ruthruff | Catalytic polymerization of unsaturated organic compounds |
US2407494A (en) * | 1941-01-02 | 1946-09-10 | Jasco Inc | Low-temperature process of polymerizing isoolefinic material |
US2411097A (en) * | 1944-03-16 | 1946-11-12 | American Locomotive Co | Heat exchanger |
US2559062A (en) * | 1945-11-27 | 1951-07-03 | Standard Oil Dev Co | Friedel-crafts metal halide-ether complexes as polymerization catalysts |
US2559984A (en) * | 1947-11-21 | 1951-07-10 | Gulf Research Development Co | Process of preparing polymeric lubricating oils |
US2727022A (en) * | 1952-04-16 | 1955-12-13 | Standard Oil Co | Process for polymerizing iso-olefin polymers with isopentane diluent |
US2833840A (en) * | 1954-06-21 | 1958-05-06 | Exxon Research Engineering Co | Process for contacting immiscible liquids |
US2856395A (en) * | 1954-05-12 | 1958-10-14 | Monsanto Chemicals | Control of polyethylene process |
US2889370A (en) * | 1955-05-18 | 1959-06-02 | Callery Chemical Co | Production of alkanol-boron fluoride complex |
US2918508A (en) * | 1957-12-02 | 1959-12-22 | Standard Oil Co | Polyisobutylene production |
US3024226A (en) * | 1959-11-23 | 1962-03-06 | Texaco Inc | Polymerization process |
US3166546A (en) * | 1961-06-09 | 1965-01-19 | Texaco Inc | Vapor phase process for the polymerization of isobutylene |
US3284537A (en) * | 1965-01-14 | 1966-11-08 | Stratford Eng Corp | Method of charging reactants through concentric feed tubes |
US3306907A (en) * | 1963-04-29 | 1967-02-28 | Standard Oil Co | Process for preparing n n-di |
US3346354A (en) * | 1963-07-02 | 1967-10-10 | Chvron Res Company | Long-chain alkenyl succinic acids, esters, and anhydrides as fuel detergents |
US3382291A (en) * | 1965-04-23 | 1968-05-07 | Mobil Oil Corp | Polymerization of olefins with bf3 |
US3634383A (en) * | 1969-07-28 | 1972-01-11 | Nasa | Method of forming difunctional polyisobutylene |
US3726842A (en) * | 1970-04-18 | 1973-04-10 | J Zizlsperger | Manufacture of modified ethylene polymers |
US3778487A (en) * | 1970-07-06 | 1973-12-11 | Sun Research Development | Polyisobutylene oil having a high viscosity index |
US3780128A (en) * | 1971-11-03 | 1973-12-18 | Ethyl Corp | Synthetic lubricants by oligomerization and hydrogenation |
US3849085A (en) * | 1972-05-08 | 1974-11-19 | Texaco Inc | Motor fuel composition |
US3935249A (en) * | 1973-05-10 | 1976-01-27 | Standard Oil Company | Tar reduction by inorganic halide for reaction of unsaturated anhydride and polybutene |
US3991129A (en) * | 1974-09-23 | 1976-11-09 | Cosden Technology, Inc. | Production of polybutene with static mixer |
US4110521A (en) * | 1977-09-21 | 1978-08-29 | Calgon Corporation | Continuous polymerization apparatus and process |
US4152499A (en) * | 1977-01-22 | 1979-05-01 | Basf Aktiengesellschaft | Polyisobutenes |
US4227027A (en) * | 1979-11-23 | 1980-10-07 | Allied Chemical Corporation | Recyclable boron trifluoride catalyst and method of using same |
US4231759A (en) * | 1973-03-12 | 1980-11-04 | Standard Oil Company (Indiana) | Liquid hydrocarbon fuels containing high molecular weight Mannich bases |
US4311808A (en) * | 1979-10-05 | 1982-01-19 | Union Carbide Canada Limited | Cling film composition of olefin polymer blend |
US4383093A (en) * | 1980-06-04 | 1983-05-10 | Mitsui Petrochemical Industries Ltd. | Tubular polymerization reactor, and process for polymerization |
US4391959A (en) * | 1980-03-21 | 1983-07-05 | Basf Aktiengesellschaft | Polymerization of isobutylene |
US4400493A (en) * | 1982-04-07 | 1983-08-23 | Cosden Technology, Inc. | Polymerization of isobutylene |
US4429099A (en) * | 1982-11-22 | 1984-01-31 | The University Of Akron | Phenol terminated polymers and epoxies therefrom |
US4433197A (en) * | 1982-07-08 | 1984-02-21 | Gulf Research & Development Company | Removing boron trifluoride from coordination compound contaminants in organic liquids |
US4465819A (en) * | 1980-03-10 | 1984-08-14 | Occidental Chemical Corporation | Semi or fully continuous process for polyester of bisphenol and dicarboxylic acid by transesterification polymerization and product thereof |
US4605808A (en) * | 1983-11-01 | 1986-08-12 | Bp Chemicals Limited | Cationic polymerization of 1-olefins |
US4663406A (en) * | 1985-03-15 | 1987-05-05 | Basf Aktiengesellschaft | Catalyst systems for the cationic polymerization of isobutylene |
US4691072A (en) * | 1985-08-01 | 1987-09-01 | Basf Aktiengesellschaft | Polymerization of isobutylene |
US4849572A (en) * | 1987-12-22 | 1989-07-18 | Exxon Chemical Patents Inc. | Process for preparing polybutenes having enhanced reactivity using boron trifluoride catalysts (PT-647) |
US4862702A (en) * | 1987-03-02 | 1989-09-05 | Neal Andrew W O | Head pressure control system for refrigeration unit |
US4883847A (en) * | 1988-10-27 | 1989-11-28 | Amoco Corporation | Process to terminate an olefin polymerization reaction |
US4914166A (en) * | 1988-01-20 | 1990-04-03 | The University Of Akron | Non-fouling liquid nitrogen cooled polymerization process |
US4943616A (en) * | 1988-07-26 | 1990-07-24 | Polysar Limited | Living cationic polymerization process |
US4956512A (en) * | 1987-11-12 | 1990-09-11 | Neste Oy | Procedure for producing poly-alpha-olefine-type lubricants |
US4973733A (en) * | 1987-02-09 | 1990-11-27 | Texaco Inc. | Method of functionalizing polymers |
US4982042A (en) * | 1988-10-17 | 1991-01-01 | Idemitsu Petrochemical Co., Ltd. | Process for manufacture of olefin oligomer |
US5068490A (en) * | 1989-08-18 | 1991-11-26 | Amoco Corporation | BF3-tertiary etherate complexes for isobutylene polymerization |
US5191044A (en) * | 1990-10-19 | 1993-03-02 | Basf Aktiengesellschaft | Preparation of polyisobutene |
US5192335A (en) * | 1992-03-20 | 1993-03-09 | Chevron Research And Technology Company | Fuel additive compositions containing poly(oxyalkylene) amines and polyalkyl hydroxyaromatics |
US5254784A (en) * | 1990-12-21 | 1993-10-19 | Neste Oy | Method for recovering a gaseous boron trifluoride bf3 and the usage of the product formed in the method |
US5254649A (en) * | 1990-11-28 | 1993-10-19 | Bp Chemicals Limited | Cationic polymerization of 1-olefins |
US5286823A (en) * | 1991-06-22 | 1994-02-15 | Basf Aktiengesellschaft | Preparation of highly reactive polyisobutenes |
US5300701A (en) * | 1992-12-28 | 1994-04-05 | Chevron Research And Technology Company | Process for the preparation of polyisobutyl hydroxyaromatics |
US5439991A (en) * | 1993-06-30 | 1995-08-08 | Bp Chemicals Limited | Method of mixing heterogeneous systems |
US5448001A (en) * | 1994-10-07 | 1995-09-05 | Queen's University At Kingston | Polymerization of iso-butylene |
US5556932A (en) * | 1993-03-02 | 1996-09-17 | Basf Aktiengesellschaft | Chlorine-free, non-drying isobutene/diene copolymers and process for their preparation |
US5563313A (en) * | 1991-06-28 | 1996-10-08 | Exxon Chemical Patents Inc. | Immobilized Lewis Acid catalysts |
US5710225A (en) * | 1996-08-23 | 1998-01-20 | The Lubrizol Corporation | Heteropolyacid catalyzed polymerization of olefins |
US5731379A (en) * | 1997-01-03 | 1998-03-24 | Dow Corning Corporation | Copolymers of polyorganosiloxane, polyisobutylene, and alkyl acrylates or methacrylates |
US5733993A (en) * | 1996-11-14 | 1998-03-31 | Ethyl Corporation | Polymeric dispersants via novel terpolymers |
US5767334A (en) * | 1994-06-24 | 1998-06-16 | Neste Alfa Oy | Method for removing catalyst from an oligomer product |
US5779742A (en) * | 1996-08-08 | 1998-07-14 | The Lubrizol Corporation | Acylated nitrogen compounds useful as additives for lubricating oil and fuel compositions |
US5792729A (en) * | 1996-08-20 | 1998-08-11 | Chevron Chemical Corporation | Dispersant terpolymers |
US5811616A (en) * | 1995-06-13 | 1998-09-22 | Amoco Corporation | BF3 gas recovery process |
US5910550A (en) * | 1996-05-13 | 1999-06-08 | Basf Aktiengesellschaft | Preparation of medium molecular weight, highly reactive polyisobutene |
US5945575A (en) * | 1995-08-07 | 1999-08-31 | Sigwart; Christoph | Method of producing reactive halogen-free, polyisobutene |
US5962604A (en) * | 1995-06-07 | 1999-10-05 | Basf Aktiengesellschaft | Process for preparing low molecular weight, highly reactive polyisobutylene |
US5977251A (en) * | 1996-04-01 | 1999-11-02 | The Dow Chemical Company | Non-adiabatic olefin solution polymerization |
US6132827A (en) * | 1997-05-19 | 2000-10-17 | Aep Industries, Inc. | Tacky stretch film and method of making and using the same |
US6300444B1 (en) * | 1998-08-25 | 2001-10-09 | Nippon Petrochemicals Company, Limited | Process for producing butene polymer |
US6361856B1 (en) * | 1995-12-28 | 2002-03-26 | Gunze Limited | Easily tearable film |
US6384154B1 (en) * | 1998-07-31 | 2002-05-07 | Basf Aktiengesellschaft | Preparation of halogen-free, reactive polyisobutene |
US6407186B1 (en) * | 1997-12-12 | 2002-06-18 | Basf Aktiengesellschaft | Method for producing low-molecular, highly reactive polyisobutylene |
US6441110B1 (en) * | 1997-02-06 | 2002-08-27 | Basf Aktiengesellschaft | Method for producing halogen-free reactive polyisobutene |
US6479598B1 (en) * | 1999-07-20 | 2002-11-12 | Exxonmobil Chemical Patents Inc. | Petroleum resins and their production with BF3 catalyst |
US6518373B1 (en) * | 1999-10-28 | 2003-02-11 | Basf Aktiengesellschaft | Method for producing highly reactive polyisobutenes |
US6525149B1 (en) * | 1999-09-16 | 2003-02-25 | Texas Petrochemicals, Lp | Process for preparing polyolefin products |
US20030040587A1 (en) * | 2001-03-28 | 2003-02-27 | Texas Petrochemicals Lp | Mid-range vinylidene content polyisobutylene polymer product and process for producing the same |
US6562913B1 (en) * | 1999-09-16 | 2003-05-13 | Texas Petrochemicals Lp | Process for producing high vinylidene polyisobutylene |
US20030162918A1 (en) * | 2000-08-16 | 2003-08-28 | Thomas Wettling | Method for producing polyisobutenes |
US20030191257A1 (en) * | 2000-07-18 | 2003-10-09 | Thomas Wettling | Method for producing polyisobutylenes |
US6642239B2 (en) * | 2000-02-10 | 2003-11-04 | Novartis Ag | Dipeptide nitrile cathepsin K inhibitors |
US6777506B1 (en) * | 2003-05-09 | 2004-08-17 | Texas Petrochemicals, Lp | Apparatus for preparing polyolefin products and methodology for using the same |
US6884858B2 (en) * | 1999-10-19 | 2005-04-26 | Texas Petrochemicals Lp | Process for preparing polyolefin products |
US6992152B2 (en) * | 1999-10-19 | 2006-01-31 | Texas Petrochemicals Lp | Apparatus and method for controlling olefin polymerization process |
US7049363B2 (en) * | 2000-05-30 | 2006-05-23 | Daimlerchyrsler Ag | Material system for use in three dimensional printing |
US7105616B2 (en) * | 2001-04-11 | 2006-09-12 | Basf Aktiengesellschaft | Separation of isobutene non-reacted during polymerization of isobutene |
US7441104B2 (en) * | 2002-03-30 | 2008-10-21 | Hewlett-Packard Development Company, L.P. | Parallel subword instructions with distributed results |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2815335A (en) | 1952-08-29 | 1957-12-03 | Exxon Research Engineering Co | Divinyl benzene modified polymers |
US2775577A (en) * | 1952-12-23 | 1956-12-25 | Exxon Research Engineering Co | Controlled isobutylene polymerization |
US2852500A (en) | 1954-06-01 | 1958-09-16 | Exxon Research Engineering Co | Controlling feed for styrene-isobutylene copolymer manufacture by adjusting specificgravity |
GB1159368A (en) | 1965-09-02 | 1969-07-23 | Standard Oil Co | Substituted Phenols |
US3927041A (en) | 1973-10-01 | 1975-12-16 | Standard Oil Co | Process of making alkenyl succinic anhydride |
US4242531A (en) | 1978-08-14 | 1980-12-30 | Phillips Petroleum Company | Olefin dimerization |
US4238628A (en) | 1978-09-28 | 1980-12-09 | Standard Oil Company (Indiana) | Polyalkylaromatics undegraded during alkylation |
DE3300155A1 (en) | 1983-01-05 | 1984-07-05 | Basf Ag, 6700 Ludwigshafen | METHOD FOR THE CONTINUOUS PRODUCTION OF ISOBUTYLENE POLYMERISATS |
DE3576462D1 (en) | 1984-02-10 | 1990-04-19 | Tmc Corp | HEEL REST. |
CH666279A5 (en) | 1985-10-03 | 1988-07-15 | Bashkirsky G Uni Im 40 Letia O | METHOD FOR PRODUCING ISOBUTYLENE POLYMERS AND DEVICE FOR CARRYING OUT THIS METHOD. |
DE3611230A1 (en) | 1986-04-04 | 1987-10-08 | Basf Ag | POLYBUTYL AND POLYISOBUTYLAMINE, METHOD FOR THE PRODUCTION THEREOF AND THE FUEL AND LUBRICANT COMPOSITIONS CONTAINING THE SAME |
JPH0651752B2 (en) | 1987-02-20 | 1994-07-06 | 鐘淵化学工業株式会社 | Process for producing isobutylene-based polymer having functional end |
CA1336281C (en) | 1988-07-26 | 1995-07-11 | Munmaya Kumar Mishra | Polymerization process and catalyst system therefor |
GB8912271D0 (en) | 1989-05-27 | 1989-07-12 | Bp Chem Int Ltd | Cationic polymerisation of 1-olefins |
US5175225A (en) | 1989-09-29 | 1992-12-29 | Chevron Research And Technology Company | Process for preparing polymeric dispersants having alternating polyalkylene and succinic groups |
DE4033195A1 (en) | 1990-10-19 | 1992-04-23 | Basf Ag | METHOD FOR PRODUCING POLYISOBUTES |
WO1993010063A1 (en) | 1991-11-18 | 1993-05-27 | Amoco Corporation | Bf3-tertiary etherate complexes for isobutylene polymerization |
GB9404368D0 (en) | 1994-03-07 | 1994-04-20 | Bp Chem Int Ltd | Production of polyisobutenes |
DE4425834A1 (en) | 1994-07-21 | 1996-01-25 | Basf Ag | Reaction products made of polyisobutenes and nitrogen oxides or mixtures of nitrogen oxides and oxygen and their use as fuel and lubricant additives |
US6075174A (en) | 1995-05-08 | 2000-06-13 | Bp Amoco Corporation | BF3 removal from BF3 catalyzed olefin oligomer |
GB9618546D0 (en) | 1996-09-05 | 1996-10-16 | Bp Chemicals Additives | Dispersants/detergents for hydrocarbons fuels |
DE19825334A1 (en) | 1998-06-05 | 1999-12-09 | Basf Ag | Process for the production of highly reactive polyisobutenes |
FR2794757B1 (en) | 1999-06-11 | 2002-06-14 | Bp Chemicals Snc | PROCESS FOR THE POLYMERIZATION OF ISOBUTENE |
DE19948947A1 (en) | 1999-10-11 | 2001-04-12 | Basf Ag | Process for the continuous production of polyisobutenes |
DE19952030A1 (en) | 1999-10-28 | 2001-05-03 | Basf Ag | Process for the production of highly reactive polyisobutenes |
DE10021377C2 (en) | 2000-05-02 | 2002-03-07 | Franz Binder Gmbh & Co Elek Sc | circular Connectors |
FR2810325A1 (en) | 2000-06-16 | 2001-12-21 | Bp Chemicals Snc | Process for maintaining property of polyisobutene during polymerization, involves calculating mean value of property of polymer from calculated instantaneous value obtained by measuring concentration of isobutene |
AU2003213037B2 (en) * | 2002-02-15 | 2006-12-14 | Zms, Llc | Polymerization process and materials for biomedical applications |
-
2009
- 2009-05-19 US US12/468,195 patent/US20100298507A1/en not_active Abandoned
-
2010
- 2010-04-05 KR KR1020117030211A patent/KR20120026552A/en not_active Application Discontinuation
- 2010-04-05 WO PCT/US2010/029892 patent/WO2010135034A1/en active Application Filing
- 2010-04-05 EP EP10778074A patent/EP2432806A4/en not_active Withdrawn
- 2010-04-05 CN CN2010800323328A patent/CN102803300A/en active Pending
- 2010-04-16 TW TW099112005A patent/TW201041903A/en unknown
- 2010-05-17 SA SA110310388A patent/SA110310388B1/en unknown
-
2011
- 2011-03-08 US US12/932,837 patent/US9809665B2/en active Active
Patent Citations (99)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US132264A (en) * | 1872-10-15 | Improvement in treating ammoniacal liquors of gas-works,gc | ||
US2139038A (en) * | 1935-02-07 | 1938-12-06 | Standard Oil Dev Co | Process for producing polymers of olefines |
US2379656A (en) * | 1940-08-23 | 1945-07-03 | Robert F Ruthruff | Catalytic polymerization of unsaturated organic compounds |
US2407494A (en) * | 1941-01-02 | 1946-09-10 | Jasco Inc | Low-temperature process of polymerizing isoolefinic material |
US2411097A (en) * | 1944-03-16 | 1946-11-12 | American Locomotive Co | Heat exchanger |
US2559062A (en) * | 1945-11-27 | 1951-07-03 | Standard Oil Dev Co | Friedel-crafts metal halide-ether complexes as polymerization catalysts |
US2559984A (en) * | 1947-11-21 | 1951-07-10 | Gulf Research Development Co | Process of preparing polymeric lubricating oils |
US2727022A (en) * | 1952-04-16 | 1955-12-13 | Standard Oil Co | Process for polymerizing iso-olefin polymers with isopentane diluent |
US2856395A (en) * | 1954-05-12 | 1958-10-14 | Monsanto Chemicals | Control of polyethylene process |
US2833840A (en) * | 1954-06-21 | 1958-05-06 | Exxon Research Engineering Co | Process for contacting immiscible liquids |
US2889370A (en) * | 1955-05-18 | 1959-06-02 | Callery Chemical Co | Production of alkanol-boron fluoride complex |
US2918508A (en) * | 1957-12-02 | 1959-12-22 | Standard Oil Co | Polyisobutylene production |
US3024226A (en) * | 1959-11-23 | 1962-03-06 | Texaco Inc | Polymerization process |
US3166546A (en) * | 1961-06-09 | 1965-01-19 | Texaco Inc | Vapor phase process for the polymerization of isobutylene |
US3306907A (en) * | 1963-04-29 | 1967-02-28 | Standard Oil Co | Process for preparing n n-di |
US3346354A (en) * | 1963-07-02 | 1967-10-10 | Chvron Res Company | Long-chain alkenyl succinic acids, esters, and anhydrides as fuel detergents |
US3284537A (en) * | 1965-01-14 | 1966-11-08 | Stratford Eng Corp | Method of charging reactants through concentric feed tubes |
US3382291A (en) * | 1965-04-23 | 1968-05-07 | Mobil Oil Corp | Polymerization of olefins with bf3 |
US3634383A (en) * | 1969-07-28 | 1972-01-11 | Nasa | Method of forming difunctional polyisobutylene |
US3726842A (en) * | 1970-04-18 | 1973-04-10 | J Zizlsperger | Manufacture of modified ethylene polymers |
US3778487A (en) * | 1970-07-06 | 1973-12-11 | Sun Research Development | Polyisobutylene oil having a high viscosity index |
US3780128A (en) * | 1971-11-03 | 1973-12-18 | Ethyl Corp | Synthetic lubricants by oligomerization and hydrogenation |
US3849085A (en) * | 1972-05-08 | 1974-11-19 | Texaco Inc | Motor fuel composition |
US4231759A (en) * | 1973-03-12 | 1980-11-04 | Standard Oil Company (Indiana) | Liquid hydrocarbon fuels containing high molecular weight Mannich bases |
US3935249A (en) * | 1973-05-10 | 1976-01-27 | Standard Oil Company | Tar reduction by inorganic halide for reaction of unsaturated anhydride and polybutene |
US3991129A (en) * | 1974-09-23 | 1976-11-09 | Cosden Technology, Inc. | Production of polybutene with static mixer |
US4152499A (en) * | 1977-01-22 | 1979-05-01 | Basf Aktiengesellschaft | Polyisobutenes |
US4110521A (en) * | 1977-09-21 | 1978-08-29 | Calgon Corporation | Continuous polymerization apparatus and process |
US4311808A (en) * | 1979-10-05 | 1982-01-19 | Union Carbide Canada Limited | Cling film composition of olefin polymer blend |
US4227027A (en) * | 1979-11-23 | 1980-10-07 | Allied Chemical Corporation | Recyclable boron trifluoride catalyst and method of using same |
US4465819A (en) * | 1980-03-10 | 1984-08-14 | Occidental Chemical Corporation | Semi or fully continuous process for polyester of bisphenol and dicarboxylic acid by transesterification polymerization and product thereof |
US4391959A (en) * | 1980-03-21 | 1983-07-05 | Basf Aktiengesellschaft | Polymerization of isobutylene |
US4383093A (en) * | 1980-06-04 | 1983-05-10 | Mitsui Petrochemical Industries Ltd. | Tubular polymerization reactor, and process for polymerization |
US4400493A (en) * | 1982-04-07 | 1983-08-23 | Cosden Technology, Inc. | Polymerization of isobutylene |
US4433197A (en) * | 1982-07-08 | 1984-02-21 | Gulf Research & Development Company | Removing boron trifluoride from coordination compound contaminants in organic liquids |
US4429099A (en) * | 1982-11-22 | 1984-01-31 | The University Of Akron | Phenol terminated polymers and epoxies therefrom |
US4605808A (en) * | 1983-11-01 | 1986-08-12 | Bp Chemicals Limited | Cationic polymerization of 1-olefins |
US4663406A (en) * | 1985-03-15 | 1987-05-05 | Basf Aktiengesellschaft | Catalyst systems for the cationic polymerization of isobutylene |
US4691072A (en) * | 1985-08-01 | 1987-09-01 | Basf Aktiengesellschaft | Polymerization of isobutylene |
US4973733A (en) * | 1987-02-09 | 1990-11-27 | Texaco Inc. | Method of functionalizing polymers |
US4862702A (en) * | 1987-03-02 | 1989-09-05 | Neal Andrew W O | Head pressure control system for refrigeration unit |
US4956512A (en) * | 1987-11-12 | 1990-09-11 | Neste Oy | Procedure for producing poly-alpha-olefine-type lubricants |
US4849572A (en) * | 1987-12-22 | 1989-07-18 | Exxon Chemical Patents Inc. | Process for preparing polybutenes having enhanced reactivity using boron trifluoride catalysts (PT-647) |
US4914166A (en) * | 1988-01-20 | 1990-04-03 | The University Of Akron | Non-fouling liquid nitrogen cooled polymerization process |
US4943616A (en) * | 1988-07-26 | 1990-07-24 | Polysar Limited | Living cationic polymerization process |
US4982042A (en) * | 1988-10-17 | 1991-01-01 | Idemitsu Petrochemical Co., Ltd. | Process for manufacture of olefin oligomer |
US4883847A (en) * | 1988-10-27 | 1989-11-28 | Amoco Corporation | Process to terminate an olefin polymerization reaction |
US5068490A (en) * | 1989-08-18 | 1991-11-26 | Amoco Corporation | BF3-tertiary etherate complexes for isobutylene polymerization |
US5191044A (en) * | 1990-10-19 | 1993-03-02 | Basf Aktiengesellschaft | Preparation of polyisobutene |
US5254649A (en) * | 1990-11-28 | 1993-10-19 | Bp Chemicals Limited | Cationic polymerization of 1-olefins |
US5254784A (en) * | 1990-12-21 | 1993-10-19 | Neste Oy | Method for recovering a gaseous boron trifluoride bf3 and the usage of the product formed in the method |
US5286823A (en) * | 1991-06-22 | 1994-02-15 | Basf Aktiengesellschaft | Preparation of highly reactive polyisobutenes |
US5408018A (en) * | 1991-06-22 | 1995-04-18 | Basf Aktiengesellschaft | Preparation of highly reactive polyisobutenes |
US5563313A (en) * | 1991-06-28 | 1996-10-08 | Exxon Chemical Patents Inc. | Immobilized Lewis Acid catalysts |
US5192335A (en) * | 1992-03-20 | 1993-03-09 | Chevron Research And Technology Company | Fuel additive compositions containing poly(oxyalkylene) amines and polyalkyl hydroxyaromatics |
US5300701A (en) * | 1992-12-28 | 1994-04-05 | Chevron Research And Technology Company | Process for the preparation of polyisobutyl hydroxyaromatics |
US5556932A (en) * | 1993-03-02 | 1996-09-17 | Basf Aktiengesellschaft | Chlorine-free, non-drying isobutene/diene copolymers and process for their preparation |
US5439991A (en) * | 1993-06-30 | 1995-08-08 | Bp Chemicals Limited | Method of mixing heterogeneous systems |
US5767334A (en) * | 1994-06-24 | 1998-06-16 | Neste Alfa Oy | Method for removing catalyst from an oligomer product |
US5448001A (en) * | 1994-10-07 | 1995-09-05 | Queen's University At Kingston | Polymerization of iso-butylene |
US5962604A (en) * | 1995-06-07 | 1999-10-05 | Basf Aktiengesellschaft | Process for preparing low molecular weight, highly reactive polyisobutylene |
US5811616A (en) * | 1995-06-13 | 1998-09-22 | Amoco Corporation | BF3 gas recovery process |
US5945575A (en) * | 1995-08-07 | 1999-08-31 | Sigwart; Christoph | Method of producing reactive halogen-free, polyisobutene |
US6361856B1 (en) * | 1995-12-28 | 2002-03-26 | Gunze Limited | Easily tearable film |
US5977251A (en) * | 1996-04-01 | 1999-11-02 | The Dow Chemical Company | Non-adiabatic olefin solution polymerization |
US5910550A (en) * | 1996-05-13 | 1999-06-08 | Basf Aktiengesellschaft | Preparation of medium molecular weight, highly reactive polyisobutene |
US5779742A (en) * | 1996-08-08 | 1998-07-14 | The Lubrizol Corporation | Acylated nitrogen compounds useful as additives for lubricating oil and fuel compositions |
US5792729A (en) * | 1996-08-20 | 1998-08-11 | Chevron Chemical Corporation | Dispersant terpolymers |
US5710225A (en) * | 1996-08-23 | 1998-01-20 | The Lubrizol Corporation | Heteropolyacid catalyzed polymerization of olefins |
US5814706A (en) * | 1996-11-14 | 1998-09-29 | Ethyl Corporation | Polymeric dispersants via novel terpolymers |
US5733993A (en) * | 1996-11-14 | 1998-03-31 | Ethyl Corporation | Polymeric dispersants via novel terpolymers |
US5731379A (en) * | 1997-01-03 | 1998-03-24 | Dow Corning Corporation | Copolymers of polyorganosiloxane, polyisobutylene, and alkyl acrylates or methacrylates |
US6441110B1 (en) * | 1997-02-06 | 2002-08-27 | Basf Aktiengesellschaft | Method for producing halogen-free reactive polyisobutene |
US6132827A (en) * | 1997-05-19 | 2000-10-17 | Aep Industries, Inc. | Tacky stretch film and method of making and using the same |
US6407186B1 (en) * | 1997-12-12 | 2002-06-18 | Basf Aktiengesellschaft | Method for producing low-molecular, highly reactive polyisobutylene |
US6384154B1 (en) * | 1998-07-31 | 2002-05-07 | Basf Aktiengesellschaft | Preparation of halogen-free, reactive polyisobutene |
US6300444B1 (en) * | 1998-08-25 | 2001-10-09 | Nippon Petrochemicals Company, Limited | Process for producing butene polymer |
US6479598B1 (en) * | 1999-07-20 | 2002-11-12 | Exxonmobil Chemical Patents Inc. | Petroleum resins and their production with BF3 catalyst |
US6562913B1 (en) * | 1999-09-16 | 2003-05-13 | Texas Petrochemicals Lp | Process for producing high vinylidene polyisobutylene |
US6525149B1 (en) * | 1999-09-16 | 2003-02-25 | Texas Petrochemicals, Lp | Process for preparing polyolefin products |
US6683138B2 (en) * | 1999-09-16 | 2004-01-27 | Texas Petrochemicals Lp | Process for producing high vinylidene polyisobutylene |
US6992152B2 (en) * | 1999-10-19 | 2006-01-31 | Texas Petrochemicals Lp | Apparatus and method for controlling olefin polymerization process |
US7056990B2 (en) * | 1999-10-19 | 2006-06-06 | Texas Petrochemicals, Lp | Process for producing mid-range vinylidene content polyisobutylene polymer products |
US7498396B2 (en) * | 1999-10-19 | 2009-03-03 | Texas Petrochemicals Lp | Mid-range vinylidene content polyisobutylene polymer product produced by liquid phase polymerization process |
US6884858B2 (en) * | 1999-10-19 | 2005-04-26 | Texas Petrochemicals Lp | Process for preparing polyolefin products |
US6518373B1 (en) * | 1999-10-28 | 2003-02-11 | Basf Aktiengesellschaft | Method for producing highly reactive polyisobutenes |
US6642239B2 (en) * | 2000-02-10 | 2003-11-04 | Novartis Ag | Dipeptide nitrile cathepsin K inhibitors |
US7049363B2 (en) * | 2000-05-30 | 2006-05-23 | Daimlerchyrsler Ag | Material system for use in three dimensional printing |
US20030191257A1 (en) * | 2000-07-18 | 2003-10-09 | Thomas Wettling | Method for producing polyisobutylenes |
US20030162918A1 (en) * | 2000-08-16 | 2003-08-28 | Thomas Wettling | Method for producing polyisobutenes |
US7037999B2 (en) * | 2001-03-28 | 2006-05-02 | Texas Petrochemicals Lp | Mid-range vinylidene content polyisobutylene polymer product and process for producing the same |
US20030040587A1 (en) * | 2001-03-28 | 2003-02-27 | Texas Petrochemicals Lp | Mid-range vinylidene content polyisobutylene polymer product and process for producing the same |
US7091285B2 (en) * | 2001-03-28 | 2006-08-15 | Texas Petrochemicals Lp | Adducts of mid-range vinylidene content polyisobutylene polymer products and methods for making the same |
US7105616B2 (en) * | 2001-04-11 | 2006-09-12 | Basf Aktiengesellschaft | Separation of isobutene non-reacted during polymerization of isobutene |
US7441104B2 (en) * | 2002-03-30 | 2008-10-21 | Hewlett-Packard Development Company, L.P. | Parallel subword instructions with distributed results |
US6858188B2 (en) * | 2003-05-09 | 2005-02-22 | Texas Petrochemicals, Lp | Apparatus for preparing polyolefin products and methodology for using the same |
US6844400B2 (en) * | 2003-05-09 | 2005-01-18 | Texas Petrochemicals Lp | Apparatus for preparing polyolefin products and methodology for using the same |
US6844401B2 (en) * | 2003-05-09 | 2005-01-18 | Texas Petrochemicals Lp | Apparatus for preparing polyolefin products and methodology for using the same |
US6777506B1 (en) * | 2003-05-09 | 2004-08-17 | Texas Petrochemicals, Lp | Apparatus for preparing polyolefin products and methodology for using the same |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012170411A2 (en) * | 2011-06-08 | 2012-12-13 | Tpc Group L.L.C. | Production of highly reactive low molecular weight pib oligomers |
WO2012170411A3 (en) * | 2011-06-08 | 2013-04-04 | Tpc Group L.L.C. | Production of highly reactive low molecular weight pib oligomers |
US9074026B2 (en) * | 2011-10-26 | 2015-07-07 | Tpc Group Llc | Polyisobutylene prepared with low diluent content reaction medium |
KR101930736B1 (en) | 2011-10-26 | 2018-12-19 | 티피씨 그룹 엘엘씨 | Polyisobutylene prepared at high velocity and circulation rate |
WO2013062758A1 (en) * | 2011-10-26 | 2013-05-02 | Tpc Group Llc | Polyisobutylene prepared at high velocity and circulation rate |
WO2013062763A1 (en) * | 2011-10-26 | 2013-05-02 | Tpc Group Llc | Polyisobutylene prepared with low diluent content reaction medium |
US20140235810A1 (en) * | 2011-10-26 | 2014-08-21 | Tpc Group Llc | Mid-Range Vinylidene Content, High Viscosity Polyisobutylene Polymers |
KR101930735B1 (en) | 2011-10-26 | 2018-12-19 | 티피씨 그룹 엘엘씨 | Mid-range vinylidene content, high viscosity polyisobutylene polymers |
CN104024286A (en) * | 2011-10-26 | 2014-09-03 | Tpc集团有限责任公司 | Mid-range vinylidene content, high viscosity polyisobutylene polymers |
CN104024280A (en) * | 2011-10-26 | 2014-09-03 | Tpc集团有限责任公司 | Polyisobutylene Prepared At High Velocity And Circulation Rate |
US20140256891A1 (en) * | 2011-10-26 | 2014-09-11 | Tpc Group Llc | Polyisobutylene Prepared with Low Diluent Content Reaction Medium |
US9309339B2 (en) * | 2011-10-26 | 2016-04-12 | Tpc Group Llc | Mid-range vinylidene content, high viscosity polyisobutylene polymers |
WO2013062759A1 (en) * | 2011-10-26 | 2013-05-02 | Tpc Group Llc | Mid-range vinylidene content, high viscosity polyisobutylene polymers |
KR101929082B1 (en) | 2011-10-26 | 2018-12-13 | 티피씨 그룹 엘엘씨 | Polyisobutylene prepared with low diluent content reaction medium |
EP2771375A4 (en) * | 2011-10-26 | 2015-05-27 | Tpc Group Llc | Mid-range vinylidene content, high viscosity polyisobutylene polymers |
US8816028B2 (en) | 2012-05-22 | 2014-08-26 | Petrochemical Supply, Inc. | Polyisobutylene composition having internal vinylidene and process for preparing the polyisobutylene polymer composition |
WO2013192186A1 (en) * | 2012-06-18 | 2013-12-27 | Petrochemical Supply, Inc. | Polyisobutylene composition having internal vinylidene and process for preparing the polyisobutylene polymer composition |
US20150322181A1 (en) * | 2013-01-17 | 2015-11-12 | Daelim Industrial Co., Ltd. | Method for preparing polybutene |
US9683060B2 (en) * | 2013-01-17 | 2017-06-20 | Daelim Industrial Co., Ltd. | Method for preparing polybutene |
WO2017151341A1 (en) | 2016-03-03 | 2017-09-08 | Tpc Group Llc | Low-fluoride, reactive polyisobutylene |
WO2017151339A1 (en) | 2016-03-03 | 2017-09-08 | Tpc Group Llc | Low-fluoride, reactive polyisobutylene |
US9617363B1 (en) | 2016-03-03 | 2017-04-11 | Tpc Group Llc | Low-fluoride, reactive polyisobutylene |
US9617366B1 (en) | 2016-03-03 | 2017-04-11 | Tpc Group Llc | Low-fluoride, reactive polyisobutylene |
WO2019075356A3 (en) * | 2017-10-14 | 2019-07-04 | Tpc Group Llc | Non-random isobutylene copolymers |
US11208511B2 (en) | 2017-10-14 | 2021-12-28 | Tpc Group Llc | Non-random isobutylene copolymers |
Also Published As
Publication number | Publication date |
---|---|
CN102803300A (en) | 2012-11-28 |
EP2432806A4 (en) | 2012-11-07 |
US20110251359A1 (en) | 2011-10-13 |
TW201041903A (en) | 2010-12-01 |
EP2432806A1 (en) | 2012-03-28 |
US9809665B2 (en) | 2017-11-07 |
SA110310388B1 (en) | 2014-10-23 |
WO2010135034A1 (en) | 2010-11-25 |
KR20120026552A (en) | 2012-03-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9809665B2 (en) | Polyisobutylene production process with improved efficiencies and/or for forming products having improved characteristics and polyisobutylene products produced thereby | |
KR100926605B1 (en) | Mid-range vinylidene content polyisobutylene and production thereof | |
KR100600256B1 (en) | Process for preparing polyolefin products | |
JP4124788B2 (en) | Process for producing polyisobutene | |
CZ357197A3 (en) | Process for preparing low-molecular, high reacting polyisobutene | |
JP2002517575A (en) | Production of highly reactive polyisobutene | |
CN114100680A (en) | Catalyst composition and process for preparing linear alpha olefins | |
EP1678216B1 (en) | Continuous preparation of ethylene homopolymers or copolymers | |
JP4546685B2 (en) | Production of highly reactive polyisobutene | |
JP2003513120A (en) | Method for producing highly reactive polyisobutene | |
KR101974337B1 (en) | Method for producing high-molecular-weight polyisobutylene | |
EP3184557B1 (en) | Polybutene preparation method | |
CN109134719B (en) | Polymerization initiation system and process for producing highly reactive olefin functional polymers | |
JP6955474B2 (en) | Polymerization initiation system and method for producing highly reactive olefin functional polymer | |
WO2020178010A1 (en) | Polymerization process | |
US9453089B2 (en) | Production of highly reactive low molecular weight PIB oligomers | |
CN115216343B (en) | Preparation method of low-viscosity poly alpha-olefin synthetic oil | |
FI129793B (en) | Process and apparatus for producing poly-alpha-olefins | |
RU2184123C1 (en) | Method of synthesis of cis-1,4-polyisoprene | |
EP2861637B1 (en) | Polyisobutylene composition having internal vinylidene and process for preparing the polyisobutylene polymer composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: TEXAS PETROCHEMICALS LP, TEXAS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MENSCHIG, KLAUS R.;SHAIKH, SOHEL;PONNUSWAMY, SATHY R.;AND OTHERS;SIGNING DATES FROM 20090630 TO 20090702;REEL/FRAME:022988/0083 |
|
AS | Assignment |
Owner name: DEUTSCHE BANK TRUST COMPANY AMERICAS, AS COLLATERA Free format text: GRANT OF SECURITY INTEREST IN U.S. PATENTS (TERM LOAN);ASSIGNOR:TPC GROUP LLC;REEL/FRAME:024329/0236 Effective date: 20100429 Owner name: DEUTSCHE BANK TRUST COMPANY AMERICAS, AS COLLATERA Free format text: GRANT OF SECURITY INTEREST IN U.S. PATENTS (REVOLVING LOAN);ASSIGNOR:TPC GROUP LLC;REEL/FRAME:024329/0223 Effective date: 20100429 |
|
AS | Assignment |
Owner name: TEXAS PETROCHEMICALS LLC, TEXAS Free format text: CERTIFICATE OF CONVERSION;ASSIGNOR:TEXAS PETROCHEMICALS LP;REEL/FRAME:024434/0263 Effective date: 20081212 Owner name: TPC GROUP LLC, TEXAS Free format text: CHANGE OF NAME;ASSIGNOR:TEXAS PETROCHEMICALS LLC;REEL/FRAME:024434/0363 Effective date: 20100125 |
|
AS | Assignment |
Owner name: TPC GROUP LLC, TEXAS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:DEUTSCHE BANK TRUST COMPANY AMERICAS, AS COLLATERAL AGENT;REEL/FRAME:025126/0712 Effective date: 20101005 |
|
AS | Assignment |
Owner name: DEUTSCHE BANK TRUST COMPANY AMERICAS, NEW YORK Free format text: SECURITY AGREEMENT;ASSIGNOR:TPC GROUP LLC (F/K/A TEXAS PETROCHEMICALS LP);REEL/FRAME:025137/0398 Effective date: 20101005 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |
|
AS | Assignment |
Owner name: TPC GROUP LLC, TEXAS Free format text: CONFIRMATION OF TERMINATION AND RELEASE OF SECURITY INTEREST IN PATENT RIGHTS;ASSIGNOR:DEUTSCHE BANK TRUST COMPANY AMERICAS;REEL/FRAME:049949/0182 Effective date: 20190802 |