Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C2/00—Treatment of rubber solutions
  • C08C2/02—Purification
  • C08C2/04—Removal of catalyst residues
• • 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
  • C08F6/00—Post-polymerisation treatments
  • C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
• • 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

• This invention relates to a process for removing hydrogenation catalyst residue from hydrogenated polymers .
• Unsaturated polymers are hydrogenated for a variety of reasons, frequently using a nickel catalyst.
• the presence of olefinic double bonds in the polymers makes them susceptible to oxygen attack and to deterioration by actinic radiation; saturation of olefinic double bonds greatly improves environmental stability and may improve color.
• US patent No. 3,130,237 suggests hydrogenating unsaturated compounds by the use of certain cobalt complexes.
• US patent No. 3,205,218 teaches hydrogenation of olefinic compounds utilizing a complex of a nickel or cobalt compound with certain aluminum reactants .
• US patent No. 3,113,986 is related and suggests hydrogenation in the presence of the reaction products of certain metal alkoxides with aluminum trialkyls.
• hydrogenated polymers may be made that are essentially colorless (yellowness index of no more than 15, measured according to ASTM E313-73) . Accordingly, we provide a process for removing hydrogenation catalyst residue from hydrogenated polymers comprising:
• step (II) contacting the polymer cement of step (I) with one or more aqueous solution (s) of a weak acid having a pKa greater than 1.5 (determined in water at 25 °C) ;
• step (III) contacting the polymer cement of step (II) with one or more aqueous solution (s) of a weak base having a pKa smaller than 10.5;
• essentially colorless hydrogenated polymers may be produced when the residue of the hydrogenation catalysts are separated from the polymer cement by treating the latter with an aqueous solution of an inorganic acid having a pKa (relative to water) in the range of 1.5 to about 7, such as SO2 or CO2, preferably in the range of 4 to about 7 such as
• the aqueous phases resulting from the treatment with the aqueous acid solution and aqueous base solution are left with the organic phase until final separation.
• This embodiment is ideal when cost considerations are at least as important as product quality.
• the acid and base are used at relatively high concentration.
• the treated polymer cement is allowed to settle and be separated from the aqueous layer. This may be done in a conventional settler, in a coalescer or by any other means. The invention is further described in respect of this preferred embodiment.
• the aqueous acid solution may have a pH of at least 4 to 7, whereas the aqueous base solution may have a pH of at most 9 to 7.
• the amount of acid is an amount in excess of the molar amount of metal (s) to be removed.
• concentration is not critical, but in general, from 0.01 to 1 normal solutions are acceptable.
• acidic aqueous solutions having concentrations in the range of from 0.1 to 0.5 N are used.
• the polymer cement being contacted with the aqueous acid solution is preferably also contacted with an oxidizing agent.
• the oxidizing agent can be a stream of oxygen in nitrogen. About three molar percent oxygen in nitrogen is preferred. Other oxidation agents such as peroxides, may also be used.
• Mixing of the polymer cement with the aqueous acid solution is also important. Mixing with an impeller having a tip speed of greater than about 5 m/sec results in sufficient contact between the aqueous solution and the cement to result in effective removal of the metal (s).
• types of mixing other than by impeller may be used.
• a rotary dispersing unit having an interlocked structure (“CAVITRON” or "SUPRATRON") as described in Japanese patent No. 95064889 may be used, or any of the stirring blade-equipped container type mixers, static mixers, homomixers and other such line mixers described in chapter 19 of Perry's Chemical Engineers' Handbook.
• the polymer cement may be contacted with the aqueous acid solution in a volumetric ratio in the range of 0.001 to 1.0.
• This treatment may be carried out once, or -as is known to be more effective- a number of times. Purpose of this is to remove the hydrogenation catalyst residue until the level wherein it is no longer objectionable from a toxicological or polymer stability point of view. This would therefore also depend on the nature of the hydrogenation catalyst that is used.
• the polymer cement is treated with an aqueous solution of a weak base.
• Weak bases within the meaning of the present invention are the conjugated bases of the aforementioned inorganic acids.
• An example of a suitable weak base is NaHC ⁇ 3, but NaHS03 and/or a2HP04 may also be used.
• a single treatment with the aqueous base solution suffices, although two or more treatments with aqueous base solution may be carried out.
• the amount of base to be used depends on the amount of acid remaining in the polymer. Preferably the amount is in the range of 0.5 to 1.5 moles, more preferably 0.8 to 1.2 moles per mole acid.
• the concentration of the aqueous base solution is not critical, with from 0.01 to 10 normal solutions being acceptable, and from 0.1 to 0.5 normal solutions being preferred.
• one or more water washing steps may be introduced.
• the or each water layer so produced is preferably removed in the manner described herein before.
• the process of the invention may be used in respect of the hydrogenation of any unsaturated polymer.
• the polymer of the present invention is preferably a polymer derived by anionic polymerization of a diene, a mixture of dienes, or a mixture of one or more dienes with copolymerizable monomer (s) such as styrene and other vinyl aromatics.
• copolymerizable monomer such as styrene and other vinyl aromatics.
• block copolymers based on styrene and butadiene and/or isoprene exhibit thermoplastic elastomeric properties.
• Polymers that are prepared by anionic polymerization and that are then hydrogenated are typically hydrogenated in the solution or suspension (so-called polymer cement) in which they are polymerized.
• polymer cements therefore contain the metal ions used in the anionic polymerization as well, frequently at high concentrations.
• the process of the present invention also successfully removes said metal residues.
• Polymer hydrogenation catalysts useful in the present invention have been mentioned above. For instance, they include nickel alkoxide or carboxylates, such as 2-ethyl- 1-hexanoates reduced with aluminum alkyl compounds. These hydrogenation catalysts are disclosed in, for example, US patent No. 3,700,633 and 3,700,748.
• the hydrogenation may be carried out with a hydrogen partial pressure of between 0.1 and 10 MPa . More typically, the hydrogen partial pressure is between 0.7 and 8.3 MPa.
• the amount of hydrogenation catalyst may vary from 0.001 to 10 g per kg polymer. Hydrogenation can be carried out at temperatures of between 25 °C and 100 °C . The time of hydrogenation under such conditions will typically be between 0.1 and 4 hours, achieving greater than 90 percent hydrogenation of the initial olefinic unsaturation .
• the hydrogenated polymer is typically stabilized by the addition of an antioxidant or mixture of antioxidants. Frequently, a phosphorus-based stabilizer is used in combination with a sterically hindered phenolic stabilizer, such as disclosed in Japanese patent No. 94055772; or a combination of phenolic stabilizers is used, such as disclosed in Japanese patent No. 94078376. Finally, the hydrogenated polymer may be isolated and recovered by a variety of techniques. The polymer may be isolated in the form of crumbs, using the technology disclosed in US patent No. 3,202,647 or disclosed in EP patent appl . No. 731,111; by use of a cyclone separator as disclosed in US patents No.
• the copolymer was prepared in a solution of cyclohexane, using sec-butyllithium as an initiator, and sequential addition of the styrene and butadiene monomers to achieve polymerization of triblocks . After polymerization was complete, methanol was added to terminate the polymers .
• the final polymer cement contained 9 percent by weight polymer, and 44 ppm by weight lithium.
• Hydrogenation was accomplished using a catalyst prepared by adding to the polymer cement nickel 2-ethyl- 1-hexanoate reacted with triethylaluminum in a 2.2:1 molar ratio of aluminum to nickel and 250-450 ppm by weight of nickel. Hydrogen partial pressure was applied to the cement for a time period of 3.5 hours . The cement was maintained under a nitrogen blanket after hydrogenation was complete and samples of 1.5-2.5 kg of polymer cement were subjected to extraction under varying conditions to demonstrate the present invention.
• the extractions were performed in a five liter glass extraction vessel.
• the vessel contained two disk mixers equipped with 6 flat blades of 6.25 cm diameter each, and four baffles of each 1.27 cm located every 90 degrees around the inside circumference of the vessel.
• the pressure during extraction was maintained at less than 0.2 MPa at various temperatures.
• a 0.8:1 volumetric ratio of acid solution to polymer cement was added to the cement.
• the mixer was immediately started and the components were mixed for 30 minutes at 820 rpm.
• a 3 percent by volume mixture of oxygen in nitrogen was bubbled through the cement at a rate of 2-4 L/hr.
• the mixer and oxygen/nitrogen addition was stopped and the contents were allowed to phase separate for 20 minutes.
• the aqueous phase was fully drained from the extraction vessel.
• a polymer cement sample was then taken.
• the amount of nickel in the polymer was determined by inductively coupled plasma/mass spectroscopy (ICP/MS) .
• ICP/MS inductively coupled plasma/mass spectroscopy
• Examples A, B and G are comparative examples, using either a too strong acid (A, B) or lacking a treatment with a weak base (G) .

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2001
  • 2001-02-09 BR BR0108265-5A patent/BR0108265A/pt not_active Application Discontinuation
  • 2001-02-09 AU AU2001231732A patent/AU2001231732A1/en not_active Abandoned
  • 2001-02-09 MX MXPA02007680A patent/MXPA02007680A/es not_active Application Discontinuation
  • 2001-02-09 AT AT01903746T patent/ATE403681T1/de not_active IP Right Cessation
  • 2001-02-09 CN CNB018047564A patent/CN1157418C/zh not_active Expired - Fee Related
  • 2001-02-09 US US10/203,142 patent/US6800725B2/en not_active Expired - Fee Related
  • 2001-02-09 RU RU2002124140/04A patent/RU2254344C2/ru not_active IP Right Cessation
  • 2001-02-09 JP JP2001558110A patent/JP2003522258A/ja active Pending
  • 2001-02-09 DE DE60135207T patent/DE60135207D1/de not_active Expired - Fee Related
  • 2001-02-09 EP EP01903746A patent/EP1263799B1/en not_active Expired - Lifetime
  • 2001-02-09 ES ES01903746T patent/ES2311505T3/es not_active Expired - Lifetime
  • 2001-02-09 WO PCT/EP2001/001511 patent/WO2001058965A1/en not_active Ceased
  • 2001-05-07 TW TW090110842A patent/TW538061B/zh not_active IP Right Cessation
• 2002
  • 2002-08-07 ZA ZA200206302A patent/ZA200206302B/xx unknown

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