WO2000012570A1 - Removal of hydrogenation catalyst from polymer solutions by treatment with ammonia and carbon dioxide - Google Patents
Removal of hydrogenation catalyst from polymer solutions by treatment with ammonia and carbon dioxide Download PDFInfo
- Publication number
- WO2000012570A1 WO2000012570A1 PCT/EP1999/006425 EP9906425W WO0012570A1 WO 2000012570 A1 WO2000012570 A1 WO 2000012570A1 EP 9906425 W EP9906425 W EP 9906425W WO 0012570 A1 WO0012570 A1 WO 0012570A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- weight
- carbon dioxide
- ammonia
- solution
- Prior art date
Links
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
- C08F6/00—Post-polymerisation treatments
- C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
Definitions
- This invention relates to a process to prepare hydrogenated polymers. More particularly, the invention relates to the removal of residues of hydrogenation catalysts from polymer solutions. BACKGROUND OF THE INVENTION
- polymeric materials including diolefin polymers
- diolefin polymers continue to grow rapidly in such diverse areas as protective paint coverings, wire insulations, structural panels for automobiles, piping and lubricating oil viscosity index improvers.
- the stability of the polymer is of paramount importance.
- Hydrogenation of diolefin polymers greatly improves the stability of these polymers against oxidative, thermal, and ultraviolet degradation.
- Polymer hydrogenation processes have therefore been studied for many years as a method to prepare novel materials with excellent stability and other desirable properties.
- Early polymer hydrogenation processes utilized heterogeneous catalysts which were known to be useful for hydrogenation of low molecular weight olefins and aromatics . These catalyst systems included catalysts such as nickel on kieselguhr.
- a fine catalyst powder was preferred and large amounts of catalysts were required to complete the hydrogenation in a reasonable time.
- Such processes were only partially successful, since the reaction requires the diffusion of the polymer molecules into the pores of the catalyst, where the active nickel metal is present. This is a slow process when hydrogenating polymers.
- Discovery of nickel 2-ethyl-l-hexanoate/triethyl aluminum hydrogenation catalyst systems enabled rapid hydrogenation of polymers. These processes utilize the catalyst as a colloidal suspension in polymer containing solutions. This type of catalyst is referred to as a homogeneous catalyst.
- Such a process has been used for a number of years to prepare hydrogenated isoprene-styrene block copolymers that are used as viscosity index improvers in premium motor oils.
- U.S. Patent No. 3,554,991 describes an exemplary process.
- Besides nickel, Group VIII metals in general will function as the active metal in these systems, and in particular, iron, cobalt, and palladium are known
- Pore diffusion is not a limitation when homogeneous catalysts are utilized.
- the hydrogenation process is rapid and complete in a matter of minutes.
- removal of the catalyst from the polymer product is necessary because metals, particularly nickel, which remain with the polymer catalyze degradation of the polymer product.
- the removal of the catalyst from the polymer solution is commonly accomplished by the addition of an acidic aqueous solution and air to oxidize the metal, e.g. to oxidize nickel to a divalent state.
- Nickel and aluminum salts are soluble in the aqueous phase and can then be removed from the hydrogenated polymer solution by separation of the aqueous phase.
- Alternative methods to remove hydrogenation catalyst residues from solutions of hydrogenated polymers include treatment with dicarboxylic acid and an oxidant, as disclosed in U.S. Patent No. 4,595,749; treatment with an amine compound wherein the amine is either a chloride salt or a diamine having an alkyl group of 1 to 12 carbon atoms as disclosed by U.S. Patent No. 4,098,991; and treatment with a non-aqueous acid followed by neutralization with an anhydrous base and filtration, as disclosed by U.S. Patent No. 4,028,485. These processes involve contacting the polymer solution with compounds which contaminate the polymer. Further process steps can be required to remove these contaminants.
- This invention is a process comprising the steps of contacting a Group VIII metal hydrogenation catalyst residue-containing polymer solution with an aqueous solution of ammonia and carbon dioxide, separating the residue from the solution, and recovering a polymer solution preferably comprising less than 15 ppm by weight, based on polymer, of the Group VIII metal.
- the concentration of the ammonia in the aqueous solution is from 2 to 7% by weight, preferably 3 to 6% by weight.
- the concentration of the carbon dioxide in the solution is from 1 to 7% by weight, preferably 2 to 6% by weight.
- the polymer solutions of the present invention preferably comprise from 1 to 50 percent by weight of a polymer, and more preferably comprise from 5 to 40 percent by weight of polymer based on the total amount of solution.
- the polymer is a partially, selectively, or totally hydrogenated polymer.
- the present invention does not depend upon the type of nature of the polymer.
- the polymer may therefore be a thermoplastic polymer, or an elastomeric polymer and may have a molecular weight which varies between wide limits.
- Most typically, polymers which are benefited by hydrogenation are those comprising polymerized conjugated diolefins . These conjugated diolefin containing polymers are therefore preferred for the practice of the present invention.
- the copolymers may be prepared by radical, anionic or cationic polymerization and may be copolymers with other monomer units.
- the copolymers may be random, block, or tapered, and may have structures that are linear, branched, radial or star.
- the polymer is an anionically polymerized conjugated diolefin polymer which was anionically polymerized in an inert solvent and then hydrogenated in the same solvent to form the hydrogenation catalyst residue containing polymer solution.
- the preferred polymers in this invention are block copolymers of styrene and a conjugated diene, especially butadiene or isoprene.
- polymers When an anionic initiator is used, polymers will be prepared by contacting the monomers with an organoalkali metal compound in a suitable solvent at a temperature within the range from -100 °C to 300 °C, preferably at a temperature within the range from 0 °C to 100 °C.
- organoalkali metal compound having the general formula: RLi n wherein :
- R is an aliphatic, cycloaliphatic or aromatic hydrocarbon radical having from one to 20 carbon atoms; and n is an integer from 1 to .
- the polymer of the present invention is contacted with hydrogenation catalyst and hydrogen in a solution with an inert solvent such as cyclohexane, normal hexane, diethyl ether, toluene or benzene.
- the hydrogenation catalysts themselves have complex structures which are not well understood and are therefore usually described by the process used to prepare them.
- the hydrogenation catalyst can be prepared by combining a Group VIII metal carboxylate or alkoxide ("catalyst") with an alkyl or hydride of a metal selected from Groups I-A, II-A and III-B of Medeleev' s Periodic Table of Elements (“cocatalyst" ) .
- Catalyst Group VIII metal carboxylate or alkoxide
- cocatalyst an alkyl or hydride of a metal selected from Groups I-A, II-A and III-B of Medeleev' s Periodic Table of Elements
- the catalyst metals which are preferred include iron, cobalt, nickel and palladium. Nickel and cobalt are particularly preferred. Aluminum is the preferred cocatalyst metal due to the excellent activity of the resulting cocatalyst.
- the hydrogenation catalyst is extracted from the polymer cement following hydrogenation using an aqueous solution of ammonia and carbon dioxide.
- the 'aqueous solution is comprised of from 2 to 7% by weight of ammonia, preferably 3 to 6% by weight, and 1 to 7% by weight of carbon dioxide, preferably 2 to 6% by weight.
- air or oxygen is added to oxidize the metal, i.e., nickel to a divalent state.
- the hydrogenation catalyst residue-containing polymer solution is contacted with this aqueous solution either in a continuous process or in a batch process.
- the contact is preferably carried out by reacting in a stirred reactor or in an in-line mixer.
- the extraction can be carried out at a temperature of from 20 to 100 °C and an aqueous solution to polymer cement phase ratio of from 0.1 to 1.0 for a period of time from 1 to
- the polymer concentration of cement can range from 1 to 50% by weight.
- the extraction is completed by allowing the phases to separate. If the phases do not immediately separate, a phase separation agent such as isopropyl alcohol or 2-ethylhexanol is added to induce separation.
- the aqueous phase containing the extracted hydrogenation catalyst residue is removed by decantation, centrifugation, or other separation processes. Excess ammonia and carbon dioxide remaining in the polymer cement will be volatized during the finishing of the polymer subsequent to the extraction step.
- the spent extraction solution can be recycled. Devolatilization of excess ammonia and carbon dioxide from the spent extraction solution generates only water insoluble species (nickel carbonate, aluminum hydroxide and lithium carbonate, for example) which can be captured by filtration, centrifugation or other separation processes.
- the recovered water can be made up with recovered or fresh ammonia and carbon dioxide and reused.
- the extractions were performed in a baffled 5-liter extraction vessel with a height to diameter ratio of 2.2:1. Mixing was provided via a shaft fitted with two 6.35 cm (2.5" ) -diameter flat-blade turbine mixers rotating at a tip speed of 427 m/min (1400 ft/min) . Each batch extraction was carried out at a constant volume of 3.5 liters.
- the polymer solutions consisted of a hydrogenated styrene-butadiene-styrene block copolymer with number-average molecular weight of 190,000 g/mole, of which about 30% by weight is styrene, dissolved in cyclohexane at a concentration of 14% by weight.
- the solutions contained varying quantities of nickel hydrogenation catalyst as indicated in Table 1. Nickel levels were determined by atomic absorption spectroscopy.
- Example 1 Example 1
- the extraction vessel was charged with 2.0 kg of polymer solution, containing 315 ppm nickel on a dry polymer basis.
- 1.0 kg of a distilled water solution containing 5 wt% ammonia and 6 wt% carbon dioxide was charged to the vessel and the contents were heated to 50 °C.
- the mixture was stirred for 15 minutes, while a dilute stream of oxygen in nitrogen was bubbled through the reactor contents.
- the mixer was stopped and the phases were allowed to settle for 40 minutes.
- the organic phase was sampled, analyzed and determined to contain 25 ppm nickel on a dry polymer basis. Following centrifugation to remove any remaining aqueous phase, the polymer solution was determined to contain 6 ppm unextracted nickel on a dry polymer basis.
- Example 1 was repeated except for the conditions listed in Table 1.
- Example 3 Example 1 was repeated except for the conditions listed in Table 1, and the polymer content was 13 wt% in cyclohexane .
- Example 4
- Example 1 was repeated except for the conditions listed in Table 1. The two phases did not separate after mixing was stopped; 50 milliliters of isopropyl alcohol was added to the reactor contents to induce separation. Comparative Example 1
- Example 1 was repeated except the aqueous solution contained no dissolved carbon dioxide. Table 1 indicates the extraction performance was inferior when compared with Examples 1 through 4.
Landscapes
- 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)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BRPI9913223-0A BR9913223B1 (en) | 1998-08-31 | 1999-08-31 | A process for removing metal hydrogenation catalyst residue from group viii of a polymer. |
AU57437/99A AU5743799A (en) | 1998-08-31 | 1999-08-31 | Removal of hydrogenation catalyst from polymer solutions by treatment with ammonia and carbon dioxide |
AT99944576T ATE258562T1 (en) | 1998-08-31 | 1999-08-31 | REMOVAL OF HYDROGENATION CATALYSTS FROM POLYMER SOLUTIONS BY TREATMENT WITH AMMONIA AND CARBON DIOXIDE |
EP99944576A EP1115755B1 (en) | 1998-08-31 | 1999-08-31 | Removal of hydrogenation catalyst from polymer solutions by treatment with ammonia and carbon dioxide |
DE69914496T DE69914496T2 (en) | 1998-08-31 | 1999-08-31 | REMOVAL OF HYDRATION CATALYSTS FROM POLYMER SOLUTIONS BY TREATMENT WITH AMMONIA AND CARBON DIOXIDE |
JP2000567583A JP4829406B2 (en) | 1998-08-31 | 1999-08-31 | Method for removing hydrogenation catalyst by treating polymer solution with ammonia and carbon dioxide |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US9840098P | 1998-08-31 | 1998-08-31 | |
US60/098,400 | 1998-08-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000012570A1 true WO2000012570A1 (en) | 2000-03-09 |
Family
ID=22269118
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1999/006425 WO2000012570A1 (en) | 1998-08-31 | 1999-08-31 | Removal of hydrogenation catalyst from polymer solutions by treatment with ammonia and carbon dioxide |
Country Status (12)
Country | Link |
---|---|
US (1) | US6207795B1 (en) |
EP (1) | EP1115755B1 (en) |
JP (1) | JP4829406B2 (en) |
KR (1) | KR100626454B1 (en) |
AT (1) | ATE258562T1 (en) |
AU (1) | AU5743799A (en) |
BR (1) | BR9913223B1 (en) |
DE (1) | DE69914496T2 (en) |
ES (1) | ES2211160T3 (en) |
TW (1) | TWI239964B (en) |
WO (1) | WO2000012570A1 (en) |
ZA (1) | ZA200101658B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000068278A2 (en) * | 1999-05-06 | 2000-11-16 | Kraton Polymers Research B.V. | Process to prepare hydrogenated polymers with improved colour |
WO2001058965A1 (en) * | 2000-02-11 | 2001-08-16 | Kraton Polymers Research B.V. | A process for removing hydrogenation catalyst residue from hydrogenated polymers |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002308905A (en) * | 2001-04-18 | 2002-10-23 | Kuraray Co Ltd | Method for manufacturing hydrogenated diene-based polymer |
CN101704926B (en) * | 2009-11-27 | 2011-06-22 | 北京化工大学 | Method for removing noble metal catalyst in hydrogenated copolymer solution |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3531448A (en) * | 1968-11-06 | 1970-09-29 | Phillips Petroleum Co | Process for removal of hydrogenation catalyst from hyrogenated polymers |
US3780138A (en) * | 1971-09-14 | 1973-12-18 | Shell Oil Co | Method for separating metal contaminant from organic polymers |
EP0312213A1 (en) * | 1987-09-22 | 1989-04-19 | Enichem Elastomers Limited | Romoval of catalyst residues |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4098991A (en) | 1975-09-12 | 1978-07-04 | The Firestone Tire & Rubber Company | Removal of catalytic residues from hydrogenated thermoplastic or elastomeric polymers |
US4028485A (en) | 1976-01-29 | 1977-06-07 | Mobil Oil Corporation | Non-aqueous removal of soluble hydrogenation catalyst |
US4278506A (en) | 1979-12-21 | 1981-07-14 | Phillips Petroleum Company | Polymer solution purification |
US4471099A (en) | 1983-03-07 | 1984-09-11 | Phillips Petroleum Company | Treatment of a hydrogenated polymer solution after hydrogenation catalyst removal to improve subsequent lithiation reaction |
US4595749A (en) | 1984-11-23 | 1986-06-17 | Shell Oil Company | Direct removal of NI catalysts |
US4927794A (en) | 1985-06-26 | 1990-05-22 | Chevron Research Company | Leaching cobalt, molybdenum, nickel, and vanadium from spent hydroprocessing catalysts |
US5210359A (en) | 1990-01-16 | 1993-05-11 | Mobil Oil Corporation | Vulcanizable liquid compositions |
USH1303H (en) | 1990-05-24 | 1994-04-05 | Shell Oil Company | Removal of nickel catalyst from polymer solutions by water addition and centrifugation |
US5212285A (en) | 1990-06-14 | 1993-05-18 | Shell Oil Company | Removal of hydrogenation catalyst from polymer solutions by catalyzed precipitation |
US5281696A (en) | 1992-12-07 | 1994-01-25 | Shell Oil Company | Removal of hydrogenation catalyst from polymer solutions by trialkyl aluminum precipitation |
JPH0866602A (en) * | 1994-08-30 | 1996-03-12 | Nippon Zeon Co Ltd | Removing method of metallic soil |
JP3717216B2 (en) * | 1995-11-21 | 2005-11-16 | 旭化成ケミカルズ株式会社 | Process for producing block copolymer |
-
1999
- 1999-08-10 US US09/371,303 patent/US6207795B1/en not_active Expired - Lifetime
- 1999-08-31 DE DE69914496T patent/DE69914496T2/en not_active Expired - Lifetime
- 1999-08-31 AU AU57437/99A patent/AU5743799A/en not_active Abandoned
- 1999-08-31 BR BRPI9913223-0A patent/BR9913223B1/en not_active IP Right Cessation
- 1999-08-31 JP JP2000567583A patent/JP4829406B2/en not_active Expired - Fee Related
- 1999-08-31 TW TW088114895A patent/TWI239964B/en not_active IP Right Cessation
- 1999-08-31 WO PCT/EP1999/006425 patent/WO2000012570A1/en active IP Right Grant
- 1999-08-31 EP EP99944576A patent/EP1115755B1/en not_active Expired - Lifetime
- 1999-08-31 AT AT99944576T patent/ATE258562T1/en not_active IP Right Cessation
- 1999-08-31 ES ES99944576T patent/ES2211160T3/en not_active Expired - Lifetime
- 1999-08-31 KR KR1020017002552A patent/KR100626454B1/en not_active IP Right Cessation
-
2001
- 2001-02-28 ZA ZA200101658A patent/ZA200101658B/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3531448A (en) * | 1968-11-06 | 1970-09-29 | Phillips Petroleum Co | Process for removal of hydrogenation catalyst from hyrogenated polymers |
US3780138A (en) * | 1971-09-14 | 1973-12-18 | Shell Oil Co | Method for separating metal contaminant from organic polymers |
EP0312213A1 (en) * | 1987-09-22 | 1989-04-19 | Enichem Elastomers Limited | Romoval of catalyst residues |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000068278A2 (en) * | 1999-05-06 | 2000-11-16 | Kraton Polymers Research B.V. | Process to prepare hydrogenated polymers with improved colour |
US6222008B1 (en) * | 1999-05-06 | 2001-04-24 | Shell Oil Company | Treatment of polymer solution with acid and ammonia to improve polymer color |
WO2000068278A3 (en) * | 1999-05-06 | 2002-04-11 | Kraton Polymers Res Bv | Process to prepare hydrogenated polymers with improved colour |
WO2001058965A1 (en) * | 2000-02-11 | 2001-08-16 | Kraton Polymers Research B.V. | A process for removing hydrogenation catalyst residue from hydrogenated polymers |
US6800725B2 (en) | 2000-02-11 | 2004-10-05 | Kraton Polymers U.S. Llc | Process for removing hydrogenation catalyst residue from hydrogenated polymers |
Also Published As
Publication number | Publication date |
---|---|
JP4829406B2 (en) | 2011-12-07 |
TWI239964B (en) | 2005-09-21 |
AU5743799A (en) | 2000-03-21 |
BR9913223B1 (en) | 2008-11-18 |
KR20010073049A (en) | 2001-07-31 |
US6207795B1 (en) | 2001-03-27 |
ZA200101658B (en) | 2002-03-28 |
KR100626454B1 (en) | 2006-09-20 |
EP1115755B1 (en) | 2004-01-28 |
BR9913223A (en) | 2001-05-22 |
DE69914496T2 (en) | 2004-07-01 |
JP2002523573A (en) | 2002-07-30 |
ATE258562T1 (en) | 2004-02-15 |
ES2211160T3 (en) | 2004-07-01 |
DE69914496D1 (en) | 2004-03-04 |
EP1115755A1 (en) | 2001-07-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0117635A2 (en) | Improved stabilized slurries of isoolefin polymers | |
US5104972A (en) | Removal of hydrogenation catalyst from polymer solutions by contact with silicates | |
EP1214360B1 (en) | Process to prepare hydrogenated polymers with improved colour | |
EP0467429B1 (en) | Removal of hydrogenation catalyst from polymer solutions by catalyzed precipitation | |
EP0301665A2 (en) | Functionalized polymers and process for the preparation thereof | |
US5281696A (en) | Removal of hydrogenation catalyst from polymer solutions by trialkyl aluminum precipitation | |
EP1115755B1 (en) | Removal of hydrogenation catalyst from polymer solutions by treatment with ammonia and carbon dioxide | |
USH1303H (en) | Removal of nickel catalyst from polymer solutions by water addition and centrifugation | |
US5073621A (en) | Removal of group VIII metal catalyst from polymer cements by extraction with aqueous dicarboxylic acid | |
JP6080863B2 (en) | Production method of polymer, polymer solution, and polymer | |
EP1263799A1 (en) | A process for removing hydrogenation catalyst residue from hydrogenated polymers | |
US3793306A (en) | Process for removal of catalyst residues | |
US6177521B1 (en) | Hydrogenation of polymers | |
JP4503601B2 (en) | Method for partially and selectively hydrogenating polymers made with conjugated dienes | |
US6187873B1 (en) | Increased throughput in the manufacture of block copolymers by reduction in polymer cement viscosity through the addition of polar solvents | |
US5767207A (en) | Removal of lithium from polymer cements | |
USH1703H (en) | Removal of lithium from polymer cements | |
CA1092608A (en) | Method for recovering low molecular weight polymers | |
GB2308596A (en) | Removal of alkali metal from polymer cements |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1999944576 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020017002552 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2001/01658 Country of ref document: ZA Ref document number: 200101658 Country of ref document: ZA |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWP | Wipo information: published in national office |
Ref document number: 1999944576 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1020017002552 Country of ref document: KR |
|
WWG | Wipo information: grant in national office |
Ref document number: 1999944576 Country of ref document: EP |
|
WWG | Wipo information: grant in national office |
Ref document number: 1020017002552 Country of ref document: KR |