[go: up one dir, main page]

WO2004029103A1 - Procede ameliore d'hydrogenation de polymeres insatures - Google Patents

Procede ameliore d'hydrogenation de polymeres insatures Download PDF

Info

Publication number
WO2004029103A1
WO2004029103A1 PCT/US2003/029280 US0329280W WO2004029103A1 WO 2004029103 A1 WO2004029103 A1 WO 2004029103A1 US 0329280 W US0329280 W US 0329280W WO 2004029103 A1 WO2004029103 A1 WO 2004029103A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
percent
hydrogenation
polymer
component
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.)
Ceased
Application number
PCT/US2003/029280
Other languages
English (en)
Inventor
Edward M. Calverley
Avani M. Patel
Michael M. Olken
Dennis A. Hucul
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Priority to AU2003267270A priority Critical patent/AU2003267270A1/en
Publication of WO2004029103A1 publication Critical patent/WO2004029103A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/02—Hydrogenation
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation

Definitions

  • the present invention relates to a continuous hydrogenation process for hydrogenating unsaturated polymers.
  • Unsaturated polymers have been previously hydrogenated using a variety of catalysts and conditions. Historically, typical hydrogenation catalysts have low reactivity and require high catalyst to polymer ratios, especially in hydrogenation of aromatic polymers. Improvements in catalytic hydrogenation have been achieved using various metals and supports. Group VIII metals on porous supports have been particularly useful in hydrogenating unsaturated polymers, especially aromatic polymers such as described in U.S. 5,612,422. However, these catalysts have been found to have a relatively short life span in that they deactivate, for example, upon contact with polar impurities, which can be present in polymer feed streams. Additionally, previous hydrogenation processes have typically been performed as batch processes. However, batch processes are economically inefficient and product consistency is more difficult to attain.
  • WO99/64479 by Asahi discloses a method of hydrogenating vinyl aromatic- conjugated diene block copolymers using a fixed-bed reactor packed with a hydrogenation catalyst comprising a platinum group metal deposited on an inorganic support.
  • the catalyst used provides low hydrogenation rates and requires long reaction times.
  • U.S. Patent No. 6,395,841 describes a continuous process for hydrogenating an unsaturated polymer comprising contacting the unsaturated polymer with a hydrogenating agent in a fixed bed reactor, wherein the reactor is packed with a hydrogenation catalyst characterized in that the hydrogenation catalyst comprises a Group VIII metal component and at least one deactivation resistant component. While this fixed bed process works very well, it remains desirable to extend catalyst life to the greatest extent possible and thus provide a continuous process for hydrogenating unsaturated polymers at high hydrogenation rates using a catalyst which is resistant to deactivation.
  • the present invention is an improvement in the continuous process for hydrogenating an unsaturated polymer comprising contacting the unsaturated polymer with a hydrogenating agent in a fixed bed reactor, wherein the reactor is packed with a hydrogenation catalyst characterized in that the hydrogenation catalyst comprises a Group VIII metal component and at least one deactivation resistant component; wherein the improvement comprises utilizing a supported catalyst having an average pore diameter of at least 2000 A.
  • the large pore size of the supported hydrogenation catalyst in combination with a fixed bed reactor provides an improved and very efficient continuous hydrogenation process, wherein the hydrogenation rate is high, steady stable performance is achieved, and the catalyst packing is resistant to deactivation upon exposure to impurities within the polymer; thus allowing for greater productivity during the useful life of the catalyst.
  • the continuous process of the present invention hydrogenates aromatic polymers using a supported deactivation resistant hydrogenation catalyst.
  • the process of the present invention is a continuous one, wherein a composition comprising an unsaturated polymer is continuously fed into a fixed bed reactor, wherein the unsaturated polymer is hydrogenated and continuously removed from the reactor.
  • the fixed bed reactor is packed with a supported hydrogenation catalyst, herein after referred to as a supported mixed hydrogenation catalyst, characterized in that it comprises an admixture of at least two components.
  • the first component comprises any metal which will increase the rate of hydrogenation and includes nickel, cobalt, rhodium, ruthenium, palladium, platinum, other Group VIII metals, or combinations thereof.
  • rhodium and/or platinum is used.
  • the second component used in the supported mixed hydrogenation catalyst comprises a promoter which inhibits deactivation of the Group NIII metal(s) upon exposure to polar materials, and is hereinafter referred to as the deactivation resistant component.
  • Such components preferably comprise rhenium, molybdenum, tungsten, tantalum or niobium or mixtures thereof.
  • the amount of the deactivation resistant component is at least an amount which significantly inhibits the deactivation of the Group NIII metal component when exposed to polar impurities within a polymer composition, herein referred to as a deactivation inhibiting amount.
  • Deactivation of the Group VIII metal is evidenced by a significant decrease in hydrogenation reaction rate. This is exemplified in comparisons of a mixed or two component hydrogenation catalyst and a catalyst containing only a Group VIII metal component under identical conditions in the presence of a polar impurity, wherein the catalyst containing only a Group VIII metal component exhibits a hydrogenation reaction rate which is less than 75 percent of the rate achieved with the supported mixed hydrogenation catalyst.
  • the amount of deactivation resistant component is such that the ratio of the Group VIII metal component to the deactivation resistant component is from 0.5:1 to 10:1, more preferably from 1 : 1 to 7: 1 , and most preferably from 1 : 1 to 5 : 1.
  • the catalyst additionally comprises a support on which the components are deposited.
  • the support can be any material which will allow good distribution of the components and produce an efficient catalyst which can be used in the continuous process of the present invention.
  • the support will be a porous material produced from a material such as a silica, alumina, magnesium oxide or carbon, having an average pore diameter of at least 2000 A and a narrow pore size distribution.
  • the pore size distribution, pore volume, and average pore diameter of the support can be obtained via mercury porosimetry following the procedures of ASTM D- 4284-83.
  • the pore size distribution is typically measured using mercury porosimetry. However, this method is only sufficient for measuring pores of greater than 60 angstroms. Therefore, an additional method must be used to measure pores less than 60 angstroms.
  • One such method is nitrogen deso ⁇ tion according to ASTM D-4641-87 for pore diameters of less than about 600 angstroms. Therefore, narrow pore size distribution is defined as the requirement that at least 98 percent of the pore volume is defined by pores having pore diameters greater than 2000 angstroms and that the pore volume measured by nitrogen deso ⁇ tion for pores less than 2000 angstroms, be less than 2 percent of the total pore volume measured by mercury porosimetry. It has been su ⁇ risingly discovered that the use of supports having large pore diameters and narrow pore size distribution as described, are particularly advantageous in the process of the present invention.
  • the surface area can be measured according to ASTM D-3663-84.
  • the surface area is typically from 1, to 100, preferably 5 to 50 m 2 /g.
  • At least 98 percent of the pore volume is defined by pores having pore diameters greater than 1000 angstroms and that the pore volume measured by nitrogen deso ⁇ tion for pores less than 1000 angstroms, be less than 2 percent of the total pore volume measured by mercury porosimetry. In another embodiment, 98 percent of the pore volume is defined by pores having pore diameters greater than 3000 angstroms and the pore volume for pores less than 3000 angstroms is less than 2 percent of the total pore volume measured by mercury porosimetry.
  • the average pore diameter is typically at least 1000 angstroms (A), preferably at least 1500 A, and more preferably at least 2000 A.
  • the shape of the support is not particularly limited and can include spherical or cylindrical particles. Extrusion-molded supports with side cuts or ring-shaped supports can also be used.
  • the size of the catalyst in the case of spherical particles, can be from 0.2 to 10 mm in diameter; in the case of cylindrical particles, their diameters can be in the range of 0.2 to 10 mm and their lengths in the range of 0.2 to 20 mm.
  • Silica supports are preferred and can be made by combining potassium silicate in water with a gelation agent, such as formamide, polymerizing and leaching as exemplified in U.S. Patent No. 4,112,032.
  • the silica is then hydrothermally calcined as in Her, R.K., The Chemistry of Silica, John Wiley and Sons, 1979, pp. 539-544, which generally consists of heating the silica while passing a gas saturated with water over the silica for about 2 hours or more, at temperatures from 600°C to 850°C.
  • Hydrothermal calcining results in a narrowing of the pore diameter distribution as well as increasing the average pore diameter.
  • the support can be prepared by processes disclosed in Her, R.K., The Chemistry of Silica, John Wiley and Sons, 1979, pp. 510-581.
  • a silica supported catalyst can be made using the process described in U.S. Patent No. 5,110,779.
  • An appropriate metal, metal component, metal containing compound or mixtures thereof can be deposited on the support by vapor phase deposition, aqueous or nonaqueous impregnation followed by calcination, sublimation or any other conventional method, such as those exemplified in Studies in Surface Science and Catalysis. "Successful Design of Catalysts" V. 44, pg. 146-158, 1989 and Applied Heterogeneous Catalysis pgs. 75-123, Institute Francais du Petrole Publications, 1987.
  • the active metal component and the deactivation resistant component may be advantageous to deposit preferentially near the outer surface of the catalyst support.
  • catalysts with such a controlled distribution of metals may be obtained by limiting the amount of solvent used during the metals application. Any other suitable means of obtaining this non-uniform distribution would also be acceptable.
  • the appropriate metal containing compound can be any compound containing a metal, as previously described, which will produce a usable hydrogenation catalyst which is resistant to deactivation. These compounds can be salts, coordination complexes, organometallic compounds or covalent complexes.
  • the total metal content of the supported catalyst is from 0.1 to 10 wt. percent based on the total weight of the supported catalyst. Preferable amounts are from 0.2 to 8 wt. percent, more preferably 0.5 to 5 wt. percent based on total catalyst weight.
  • Promoters such as alkali, alkali earth or lanthanide containing compounds, can also be used to aid in the dispersion of the metal component onto the support or stabilization during the reaction, though their use is not preferred.
  • Polymers which can be hydrogenated by the process of the present invention include any unsaturated polymer containing olefinic or aromatic unsaturation.
  • Such polymers include hydrocarbon polymers produced from olefinic monomers, such as homopolymers of butadiene or isoprene, copolymers thereof, and aromatic polymers and copolymers.
  • Aromatic polymers which can be hydrogenated by the process of the present invention include any polymeric material containing pendant aromatic functionality.
  • Pendant aromatic functionality refers to a structure wherein the aromatic group is a substituent on the polymer backbone and not embedded therein.
  • Preferred aromatic groups are C6-20 aryl groups, especially phenyl.
  • These aromatic polymers may also contain other olefinic groups in addition to aromatic groups.
  • the aromatic polymer is derived from a monomer of the formula:
  • R is hydrogen or alkyl
  • Ar is phenyl, halophenyl, alkylphenyl, alkylhalophenyl, naphthyl, pyridinyl, or anthracenyl, wherein any alkyl group contains 1 to 6 carbon atoms which may be mono- or multisubstituted with functional groups such as halo, nitro, amino, cyano, carbonyl and carboxyl. More preferably Ar is phenyl or alkylphenyl with phenyl being most preferred. Homopolymers may have any stereostructure including syndiotactic, isotactic or atactic; however, atactic polymers are preferred.
  • copolymers containing these aromatic monomers including random, pseudo random, block, tapered block, star and grafted copolymers may also be hydrogenated.
  • copolymers of vinyl aromatic monomers and comonomers selected from nitriles, acrylates, acids, ethylene, propylene, maleic anhydride, maleimides, vinyl acetate, and vinyl chloride may also be used, such as styrene-acrylonitrile, styrene-alpha-methylstyrene and styrene-ethylene.
  • Block copolymers of vinyl aromatic monomers may also be used, such as styrene-alpha- methylstyrene block copolymers, styrene-butadiene or styrene-isoprene block copolymers and various multi-block copolymers thereof. Examples include styrene-butadiene, styrene- isoprene, styrene-butadiene-styrene and styrene-isoprene-styrene block copolymers. Further examples of block copolymers may be found in U.S.
  • Blends of polymers including impact modified, grafted rubber containing aromatic polymers may also be used.
  • the number average molecular weight (Mn) of the polymer to be hydrogenated is from 10,000 to 3,000,000, more preferably from 30,000 to 400,000, and most preferably from 50,000 to 300,000, as measured by gel permeation chromatography.
  • composition comprising the unsaturated polymer typically contains small amounts of contaminants which deactivate typical Group VIII metal hydrogenation catalysts.
  • contaminants include polymerization terminators and polar materials, and polymerization catalyst remnants such as lithium.
  • the process of the present invention allows for more efficient hydrogenation and longer catalyst life, even when hydrogenating polymer feeds containing such contaminants.
  • the continuous process of the present invention utilizes a fixed bed reactor wherein the supported catalyst is packed into the reactor and the polymer feed flows through the fixed catalyst bed.
  • Any fixed bed reactor may be used, without any particular limitations.
  • Multi-tube type reactors may be used to efficiently remove heat.
  • the liquid and gas effluents from the fixed bed may be separated and recycled to the bed again in order to make more efficient use of the hydrogen or to help control the temperature of the reactor.
  • the direction of flow of the polymer solution and the hydrogen gas may be in opposing directions or the same direction (parallel), but the parallel flow method is preferable. The direction of this flow may be upward or downward.
  • the fixed bed of supported catalyst is typically operated at a temperature of 40 to 250°C, preferably 50 to 200°C and especially preferably at 50 to 180°C.
  • the reactor can be operated adiabatically, that is, allowing the heat of reaction to be absorbed by the reacting mixture, or it may be operated using any process for heat addition and removal known in the art, including shell and tube reactors, multi-stage reactors with inter-stage heating or cooling, and cold shot addition reactors.
  • the reaction is typically performed at a hydrogen pressure of 0.5 to 20 MPa, preferably 1 to 20 MPa, and most preferably from 2 to 15 MPa, a hydrogen gas flow rate/polymer solution flow rate ratio of 20 to 700 normal liters per liter (Nl/1), preferably from 20 to 500 Nl/1 and most preferably from 40 to 350 Nl/1, and a liquid hourly space velocity (LHSV) of 0.01 to 15 (1/hr), preferably 0.03 to 10 (1/hr) and most preferably from 0.05 to 10 (1/hr).
  • LHSV is defined as the liquid feed rate in liters per hour divided by the catalyst bed volume in liters.
  • the hydrogenation reaction effluent which has reached the target hydrogenation can be separated into the hydrogen gas, solvent , and hydrogenated polymer by any method, including devolatilization and other separation techniques.
  • the hydrogenation reaction is preferably conducted in a hydrocarbon solvent in which the polymer is soluble and which will not hinder the hydrogenation reaction.
  • the solvent is a saturated solvent such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, methylcyclohexane, decalin, ethylcyclohexane, dodecane, dioxane, diethylene glycol dimethyl ether, tetrahydrofuran, isopentane, and decahydronaphthalene or mixtures thereof, with cyclohexane being the most preferred.
  • n-hexane, n-heptane and other hydrocarbons can also be used as well as mixtures with ethers, tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, alcohols, ethers or amines.
  • the polymer concentration will typically be from 5 to 30 weight percent, preferably from 5 to 25 weight percent.
  • the hydrogenation reaction is typically conducted in the absence of oxygen.
  • the reaction vessel is purged with an inert gas to remove oxygen from the reaction area prior to start up.
  • Inert gases include but are not limited to nitrogen, helium, and argon, with nitrogen being preferred.
  • the hydrogenating agent can be any hydrogen producing compound which will hydrogenate the unsaturated polymer.
  • Hydrogenating agents include but are not limited to hydrogen gas, hydrazine and sodium borohydride.
  • the hydrogenating agent is hydrogen gas.
  • the fixed bed reactor comprises a vertical reaction column packed with a granular hydrogenation catalyst.
  • a composition comprising a block copolymer is continuously passed through the column while contacted with a hydrogenating agent.
  • the direction of flow of the polymer solution and the hydrogen gas may be opposite or the same, but the parallel flow method is preferable. The direction of this flow may be upward or downward.
  • the amount of hydrogenation is dependent upon the polymer being hydrogenated, the catalyst used, the process conditions and the reaction time.
  • olefinic polymers at least 80 percent of the olefinic bonds are hydrogenated to give a hydrogenation level of 80 percent, preferably at least 90 percent, more preferably at least 95 percent and most preferably 100 percent.
  • polymers such as polystyrene and styrene-butadiene copolymers, a typical aromatic hydrogenation is greater than 80 percent (wherein greater than 80 percent of the aromatic bonds are hydrogenated), preferably greater than 99 percent, and more preferably greater than 99.5 percent. This can be determined by measuring the UV absorbance of the hydrogenated polymer and comparing to the absorbance of a non-hydrogenated standard.
  • the absorbance of a 99.5 percent hydrogenated polymer will be 99.5 percent less than the absorbance of the non-hydrogenated polymer.
  • polymers such as poly alpha- methylstyrene, styrene-alpha-methylstyrene copolymer and copolymers of a vinyl aromatic monomer and a comonomer selected from the group consisting of a nitrile, acrylate, acid, ethylene, propylene, maleic anhydride, maleimide, vinyl acetate and vinyl chloride
  • the level of hydrogenation can be lower, and is dependent upon the polymer being hydrogenated.
  • at least 20 percent aromatic hydrogenation is achieved, preferably at least 30 percent, more preferably at least 50 percent and most preferably at least 90 percent aromatic hydrogenation is achieved.
  • the amount of olefinic hydrogenation can be determined using Infrared spectroscopy or proton NMR techmques.
  • the amount of aromatic hydrogenation can be measured using UV-VTS spectroscopy. Cyclohexane solutions of polystyrene give a very distinct abso ⁇ tion band for the aromatic ring at about 260.5 nm. This band gives an absorbance of 1.000 with a solution concentration of .004980 moles of aromatic per liter in a 1 cm cell. The absorbance is dependent upon concentration.
  • the hydrogenated polymer products are typically measured at higher concentrations since they are not diluted before the absorbance is measured. Since the reaction solution is 15-30 times more concentrated than the standards, small amounts of residual unsaturation can be accurately measured.
  • the process of the present invention comprises contacting a polymer feed composition comprising at least one unsaturated polymer and at least one polar impurity, with a hydrogenation agent in the presence of a silica supported mixed hydrogenation catalyst, characterized in that the silica supported mixed hydrogenation catalyst comprises at least one Group VIII metal component and at least a deactivation inhibiting amount of at least one deactivation resistant component selected from the group consisting of a rhenium, molybdenum, tungsten, tantalum and niobium component, wherein the silica has an average pore diameter of at least 2000 A.
  • block copolymers with similar average molecular weights behave differently when undergoing hydrogenation in a fixed bed reactor with a particulate catalyst rather than a powered catalyst.
  • block copolymers rich in styrene can be hydrogenated almost completely with catalysts that have pores whose average pore diameter is at least 2000A.
  • catalysts with pores smaller than 1000A can give high conversions for short periods, their ability to sustain high conversions for long periods of time in a fixed bed reactor is limited.
  • catalysts for the hydrogenation of block copolymers that are rich in butadiene give sustained high conversions with even larger size pores compared to catalysts for polymers that are rich in styrene.
  • the amount of aromatic hydrogenation is measured using UV-VIS spectroscopy as described previously.
  • the amount of olefinic hydrogenation can be determined using Infrared spectroscopy.
  • Mn is an absolute molecular weight measured by gel permeation chromatography, unless otherwise specified.
  • a vertical jacketed stainless steel tube (76.2 cm long and 1.9 cm diameter) was loaded with 50 grams (lOOmL) of 1.2 mm x (2-8) mm cylindrical silica (Norton silica with a monomodal pore size distribution centered near 50 nanometers (nm) (500 A) pore diameter and a surface area of 65 m 2 /g) supported catalyst particles (3 wt. percent Pt and 2 wt. percent Re).
  • the reactor was operated at a temperature of 155 —185 °C and 93 bar of hydrogen pressure.
  • a polymer solution of 13 parts by weight of styrene/butadiene copolymer dissolved in 87 parts by weight of cyclohexane solvent was fed into the top of the reactor at a rate of 1.5 mL/min, giving a Liquid Hourly Space Velocity (LHSV) of 0.90. Hydrogen was fed into the tube at a rate of 190 cc/min.
  • LHSV Liquid Hourly Space Velocity
  • the conversion of the styrene was monitored using the UV-Vis absorbance at a wavelength of 259.8 nm. Samples were taken every few hours at irregular intervals and the aromatic conversion remained greater than 99 percent for the first 30 hours at which point the catalyst productivity was 5.68 grams hydrogenated polymer per gram of catalyst. The next sample was taken after 46 hours, when the catalyst had processed 8.77 grams of polymer per gram of catalyst, and the conversion had decreased to 96.9 percent.
  • Comparative Example 1 was repeated with the reactor loaded with 27 grams (100 mL) of a catalyst comprised of 3 percent Pt and 2 percent Re supported on 12-20 mesh (1.68 — 0.841 mm) granules of a silica support with a monomodal pore size distribution and an average pore diameter of 3,500 A and a BET surface area of 18 m 2 /g. Temperatures, pressures and feed flow rates were set and controlled in the same ranges as in the comparative example. Immediately upon start up the reactor achieved greater than 99 percent styrene conversion and after 120 hours on stream, the conversion was measured as 99.8 and the catalyst has hydrogenated 41.6 grams of polymer per gram of catalyst.
  • Example 1 was repeated with 27 grams of catalyst comprised of 3 percent Pt and 2 percent Re supported on 12 — 20 mesh granules of a silica support with a monomodal pore size distribution and an average pore diameter of 3,500 A and a BET surface area of 18 m /g.
  • the feed solution for this example was comprised of 12 parts by weight of a styrene-butadiene block copolymer (32 wt. percent styrene) and 88 parts by weight of cyclohexane solvent.
  • the liquid feed rate was initially set at 3 mL/min for a liquid hourly space velocity of 1.8, while the hydrogen gas was fed at 375 mL/min.
  • the reactor was loaded with 34.2 grams of a catalyst supported on a silica with an average pore diameter of 13,500 A and a BET surface area of 4 m 2 /g and loaded with 3 percent Pt and 2 percent Re by weight.
  • the feed solution for this example was comprised of 12.4 parts by weight of a styrene-butadiene block copolymer (32 wt. percent styrene) and 87.6 parts by weight of cyclohexane solvent.
  • the liquid hourly space velocity was initially set at 1.8 and later reduced to 1.2 and conversion remains above 99 percent until the productivity reached 73.3 grams of polymer per gram of catalyst. Conversion remained above 98 percent even when the productivity reached 108.8 g/g. Su ⁇ risingly, better performance and slower catalyst deactivation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne une amélioration apportée à un procédé continu d'hydrogénation d'un polymère insaturé consistant à mettre le polymère insaturé en contact avec un agent d'hydrogénation dans un réacteur à lit fixe, le réacteur étant rempli d'un catalyseur d'hydrogénation se caractérisant par le fait qu'il comprend un composant métallique du groupe VIII et au moins un composant résistant à la désactivation. L'amélioration consiste à utiliser un catalyseur d'hydrogénation supporté ayant un diamètre moyen des pores d'au moins 2000Å.
PCT/US2003/029280 2002-09-25 2003-09-16 Procede ameliore d'hydrogenation de polymeres insatures Ceased WO2004029103A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003267270A AU2003267270A1 (en) 2002-09-25 2003-09-16 Improved process for hydrogenating unsaturated polymers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US41369502P 2002-09-25 2002-09-25
US60/413,695 2002-09-25

Publications (1)

Publication Number Publication Date
WO2004029103A1 true WO2004029103A1 (fr) 2004-04-08

Family

ID=32043272

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/029280 Ceased WO2004029103A1 (fr) 2002-09-25 2003-09-16 Procede ameliore d'hydrogenation de polymeres insatures

Country Status (3)

Country Link
AU (1) AU2003267270A1 (fr)
TW (1) TW200407341A (fr)
WO (1) WO2004029103A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2147933A1 (fr) * 2008-07-24 2010-01-27 LANXESS Inc. Procédé pour l'hydrogénation continue des liaisons doubles carbone-carbone dans un polymère non saturé pour produire un polymère hydrogéné

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3338393A1 (de) * 1982-10-23 1984-04-26 Arakawa Kagaku Kogyo K.K., Osaka Verfahren zur herstellung eines hydrierten erdoelharzes
WO1999032529A1 (fr) * 1997-12-19 1999-07-01 Shell Internationale Research Maatschappij B.V. Procede d'hydrogenation de substrats organiques macromoleculaires
DE19833095A1 (de) * 1998-07-23 2000-01-27 Bayer Ag Verfahren zur Hydrierung aromatischer Polymere in Gegenwart von sauerstoffenthaltenden Kohlenwasserstoffen
DE19904612A1 (de) * 1999-02-05 2000-08-10 Bayer Ag Verfahren zur Hydrierung aromatischer Polymere in Gegenwart spezieller Katalysatoren
WO2001042319A1 (fr) * 1999-12-08 2001-06-14 The Dow Global Technologies Inc. Procede d'hydrogenation de polymeres insatures
WO2001042318A1 (fr) * 1999-12-08 2001-06-14 Dow Global Technologies Inc. Procede d'hydrogenation de polymeres aromatiques
WO2002020626A2 (fr) * 2000-09-06 2002-03-14 Dow Global Technologies Inc. Procede ameliore d'hydrogenation de polymeres non satures

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3338393A1 (de) * 1982-10-23 1984-04-26 Arakawa Kagaku Kogyo K.K., Osaka Verfahren zur herstellung eines hydrierten erdoelharzes
WO1999032529A1 (fr) * 1997-12-19 1999-07-01 Shell Internationale Research Maatschappij B.V. Procede d'hydrogenation de substrats organiques macromoleculaires
DE19833095A1 (de) * 1998-07-23 2000-01-27 Bayer Ag Verfahren zur Hydrierung aromatischer Polymere in Gegenwart von sauerstoffenthaltenden Kohlenwasserstoffen
DE19904612A1 (de) * 1999-02-05 2000-08-10 Bayer Ag Verfahren zur Hydrierung aromatischer Polymere in Gegenwart spezieller Katalysatoren
WO2001042319A1 (fr) * 1999-12-08 2001-06-14 The Dow Global Technologies Inc. Procede d'hydrogenation de polymeres insatures
WO2001042318A1 (fr) * 1999-12-08 2001-06-14 Dow Global Technologies Inc. Procede d'hydrogenation de polymeres aromatiques
WO2002020626A2 (fr) * 2000-09-06 2002-03-14 Dow Global Technologies Inc. Procede ameliore d'hydrogenation de polymeres non satures

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2147933A1 (fr) * 2008-07-24 2010-01-27 LANXESS Inc. Procédé pour l'hydrogénation continue des liaisons doubles carbone-carbone dans un polymère non saturé pour produire un polymère hydrogéné
EP2147932A1 (fr) * 2008-07-24 2010-01-27 LANXESS Inc. Procédé pour l'hydrogénation continue des liaisons doubles carbone-carbone dans un polymère non saturé pour produire un polymère hydrogéné
US8314188B2 (en) 2008-07-24 2012-11-20 Lanxess Deutschland Gmbh Process for the continuous hydrogenation of carbon-carbon double bonds in an unsaturated polymer to produce a hydrogenated polymer

Also Published As

Publication number Publication date
AU2003267270A1 (en) 2004-04-19
TW200407341A (en) 2004-05-16

Similar Documents

Publication Publication Date Title
US5612422A (en) Process for hydrogenating aromatic polymers
US6084140A (en) Catalyst for selective hydrogenation of highly unsaturated hydrocarbon compound in olefin compound
EP1240211B1 (fr) Procede d'hydrogenation de polymeres insatures
JPH02265647A (ja) ポリマー水素化触媒
EP1317492B1 (fr) Procede ameliore d'hydrogenation de polymeres non satures
EP1278782B1 (fr) Procede de preparation de polymeres aromatiques hydrogenes
US6426390B1 (en) Hydrogenated block copolymer compositions
WO2004029103A1 (fr) Procede ameliore d'hydrogenation de polymeres insatures
US6172165B1 (en) Process for hydrogenating aromatic polymers
US6455656B2 (en) Process for preparing hydrogenated aromatic polymers
US6090359A (en) Process for hydrogenating aromatic polymers
CN1175006C (zh) 在特殊的催化剂存在下氢化芳族聚合物的方法
HK1008229B (en) A process for hydrogenating aromatic polymers
WO2003025026A1 (fr) Copolymeres en bloc contenant des blocs de copolymeres aromatiques de vinyle /(alpha-alkylstyrene) hydrogenes
WO2015040095A1 (fr) Hydrogénation de polymères insaturés de bas poids moléculaire
CN117447293A (zh) 一种炔烃选择加氢方法
JPH04110304A (ja) 水素化石油樹脂の製造法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP