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
  • 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
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/22—Tin compounds
  • C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
• • 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
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/04—Monomers containing three or four carbon atoms
  • C08F210/08—Butenes
  • C08F210/10—Isobutene
  • C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber

Definitions

• the present invention relates to a polymerisation process for the preparation of isobutylene-based polymers.
• Carbocations have long been regarded as important intermediates in organic reactions but are generally too unstable to be isolable. Three types of carbocations have so far been isolated, and several of these have been structurally characterized by X-ray diffraction: (1) carbocations stabilized by heteroatoms in ⁇ -positions, notably O and N but including F and Cl; (2) carbocations with phenyl substituents; (3) tertiary-alkyl carbocations. These structural aspects have been summarized in Interactions between carbocations and anions in crystals. T. Laube, Chem. Rev. 1998, 98, 1277.
• Carbocations carrying three alkyl substituents have proved isolable in several cases. These include the parent ion CMe 3 + as Sb 2 F ⁇ salt (see: First X-ray crystallographic study of a benzyl cation, cumyl hexafluoroantimonate(V), and structural implications. T. Laube, G. A. Olah and R. Bau, J. Am. Chem. Soc. 1997, 119, 3087.) Low-temperature techniques are required to generate, crystallize and structurally characterize these compounds, which implies that their application is limited by their thermal instability and isolation techniques in SbF 5 - based media.
• cationic polymerization is effected using a catalyst system comprising: (i) a Lewis acid, (ii) a tertiary alkyl initiator molecule containing a halogen, ester, ether, acid or alcohol group, and, optionally, (iii) an electron donor molecule such as ethyl acetate.
• a catalyst system comprising: (i) a Lewis acid, (ii) a tertiary alkyl initiator molecule containing a halogen, ester, ether, acid or alcohol group, and, optionally, (iii) an electron donor molecule such as ethyl acetate.
• Such catalysts systems have been used for the so-called “living” and “non-living” carbocationic polymerization of olefins.
• Catalyst systems based on halogens and/or alkyl-containing Lewis acids, such as boron trichloride and titanium tetrachloride use
• US 5,448,001 discloses a carbocationic process for the polymerization of isobutylene which utilizes a catalyst system comprising, for example, a metallocene catalyst and a borane.
• WO-A 1-00/04061 discloses a cationic polymerization process which is conducted at subatmospheric pressure in the presence of a catalyst system such as Cp*TiMe 3 (the “initiator") and B(C F 5 ) (the “activator”). Such a system generates a “reactive cation” and a “non-coordinating anion” (NCA).
• a catalyst system such as Cp*TiMe 3 (the “initiator") and B(C F 5 ) (the “activator”
• Such a system generates a “reactive cation” and a “non-coordinating anion” (NCA).
• NCA non-coordinating anion
• NCAs disclosed in WO-A 1-00/04061 includes, boron, phosphorus and silicon compounds, including borates and bridged di-boron species.
• copolymers so produced have markedly lower molecular weights than homopolymers prepared under similar conditions. This is because the presence of isoprene in the monomer feed results in chain termination by ⁇ -H elimination.
• R is independantly hydrogen or a group of the formula M'R ] R 2 R 3 , R' is a group of the formula M'R 4 R 5 R 6 ,
• R" is hydrogen, a d to 2 alkyl, a C 6 to C ⁇ aryl or a C 7 to C 20 alkylaryl, M is Zr or Hf,
• M' is Si, Ge, Sn or Pb
• X is a halogen atom
• R 1 to R 6 is a Ci to C ⁇ 2 alkyl group, a C 6 to C ⁇ aryl or a C to C 20 alkylaryl, shows high catalytic activity in isobutene copolymerisations.
• this invention relates to the a.m. compound of the general structure (I) in itself.
• this invention relates to a catalyst of the general structure (I). In still another aspect, this invention relates to a catalytic composition comprising a compound of the a.m. general structure (I).
• this invention relates to a process for homo- or co- polymerizing isoolefines, optionally in the presence of further copolymerizable monomers, in the presence of a compound of the general structure (I).
• this invention relates to a method of stabilizing a compound of the general structure (II)
• R is a group of the formula M'R'R ⁇ 3 ,
• R" is hydrogen, a to C t2 alkyl, a C to Cj aryl or a C 7 to C 20 alkylaryl, M is Zr or Hf,
• M' is Si, Ge, Sn or Pb X is a halogen atom
• R 1 to R 3 is a Ci to C ⁇ 2 alkyl group, with a compound R' of the formula M'R 4 R 5 R 6 , in which M' is Si, Ge, Sn or Pb and R 4 to R 6 is a Ci to C, 2 alkyl group.
• this invention relates to a non-coordinating anion of the general structure [M 2 X ] " in which M is Zr or Hf and X is a halogen atom.
• Ci to C12 alkyls are known and include methyl, ethyl, linear or branched propyl, such as n-propyl, iso-propyl, linear or branched butyl, such as n-butyl, sec. butyl, tert. butyl, linear or branched pentyl, linear or branched hexyl, linear or branched heptyl, linear or branched octyl, linear or branched nonyl and so on. It will be apparent to those skilled in the art, that said Ci to C 12 alkyls may be saturated, single unsaturated or multiple unsaturated. Methyl and ethyl are preferred, methyl is especially preferred.
• Suitable C 5 to C M aryl groups are well known and include cyclopentadienyl, phenyl, naphthenyl, fluorenyl anthracenyl or phenanthryl.
• Suitable C 7 to C 20 alkylaryl groups are well known and include combinations of the mentioned d to C12 alkyls with the given C 6 to C ⁇ aryl groups such as benzyl, penta methyl cyclopentadienyl, substituted phenyl or fluorenyl groups as well as alkylaryl or arylalkyl groups not expressively mentioned in this invention.
• Suitable halogen atoms include fluorine, chlorine, bromine, iodine and mixtures thereof. It will be apparent to those skilled in the art that R 1 to R 6 may be the same or different and are chosen independently from each other.
• inventive compounds of the general structure (I) may be used alone or in combination with catalysts/initiators commonly used in isoolefin (co)polymerisation processes.
• Such compounds are known and include dialkylaluminum halides, such as diethylaluminum chloride, monoalkylaluminum dihalides, such as isobutylaluminurn dichloride, aluminoxanes, such as methylaluminoxane and mixtures thereof.
• the compound(s) of the general structure (I) are useful as catalysts, especially in a process directed to the homo- or co-polymerization of isoolefins.
• butyl rubber As used throughout this specification is intended to denote polymers prepared by reacting a major portion, e.g., from 70 to 99.5 parts by weight, usually 85 to 99.5 parts by weight of an isoolefin, such as isobutylene, with a minor portion, e.g., 30 to 0.5 parts by weight, usually 15 to 0.5 parts by weight, of a multiolefin, e.g., a conjugated diolefin, such as isoprene or butadiene, for each 100 weight parts of these monomers reacted.
• a major portion e.g., from 70 to 99.5 parts by weight, usually 85 to 99.5 parts by weight of an isoolefin, such as isobutylene
• a minor portion e.g., 30 to 0.5 parts by weight, usually 15 to 0.5 parts by weight, of a multiolefin, e.g., a conjugated diolefin, such as isoprene or buta
• the isoolefin in general, is a C to C 8 compound , e.g., isobutylene, 2-methyl-l- butene, 3-methyl- 1-butene, 2-methyl-2-butene and 4-methyl-l-pentene and mixtures thereof.
• the multiolefin in general, is a C 4 to C M diene such as isoprene, butadiene, 2- methylbutadiene, 2,4-dimethylbutadiene, piperyline, 3-methyl- 1 ,3-pentadiene, 2,4-hexadiene, 2-neopentylbutadiene, 2-methly-l,5-hexadiene, 2,5-dimethly-2,4-hexadiene, 2 -methyl- 1,4- pentadiene, 2-methyl-l,6-heptadiene, cyclopenta-diene, methylcyclopentadiene, cyclohexadiene, 1-vinyl-cyclohexadiene and mixtures thereof.
• diene such as isoprene, butadiene, 2- methylbutadiene, 2,4-dimethylbutadiene, piperyline, 3-methyl- 1 ,3-pentadiene, 2,4-hex
• the preferred monomer mixture for use in the production of butyl rubber comprises isobutylene and isoprene.
• one or more additional olefinic termonomer such as styrene, ⁇ -methylstyrene, p- methylstyrene, chlorostyrene, pentadiene and the like may be incorporated in the butyl rubber polymer. See, for example, any one of: United States patent 2,631,984; Canadian Application 2,316,741 ; United States patent 5, 162,445 ; and
• the process for producing the butyl polymer is conducted at a temperature conventional in the production of butyl polymers - e.g., in the range of from -120°C to +50°C.
• the butyl polymer may be produced by polymerization in solution or by a slurry polymerization method. Polymerization is preferably conducted in suspension (the slurry method) - see, for example, Ullmann's Encyclopedia of Industrial Chemistry (Fifth, Completely Revised Edition, Volume A23; Editors Elvers et al.).
• solvents or diluents known to the person skilled in the art for butyl polymerization may be considered as the solvents or diluents (reaction medium).
• solvents or diluents comprise alkanes, chloroalkanes, cycloalkanes or aromatics, which are frequently also mono- or polysubstituted with halogens.
• Hexane/chloroalkane mixtures, methyl chloride, dichloromethane or the mixtures thereof may be mentioned in particular.
• Chloroalkanes are preferably used in the process according to the present invention.
• the process is conducted in the presence of an aliphatic hydrocarbon diluent, such as n-hexane, and a catalyst mixture comprising a compound of the general formula (I) as stated above.
• an aliphatic hydrocarbon diluent such as n-hexane
• a catalyst mixture comprising a compound of the general formula (I) as stated above.
• Polymerization may be performed both continuously and discontinuously.
• the process is preferably performed with the following three feed streams:
• multiolefin preferably diene, isoprene
• the process may, for example, be performed as follows:
• the reactor precooled to the reaction temperature, is charged with solvent or diluent and the monomers.
• the catalyst (comprising compound of the general formula (I)), optionally together with a catalyst customary in the field of butyl polymerization, is then pumped in the form of a dilute solution in such a manner that the heat of polymerization may be dissipated without problem.
• the course of the reaction may be monitored by means of the evolution of heat. All operations are performed under protective gas.
• a phenolic antioxidant such as, for example, 2,2'-methylenebis(4-methyl-6-tert.-butylphenol), dissolved in ethanol.
• the butyl polymer prepared according to the above process may be halogenated in a conventional manner. See, for example, United States patent 5,886,106.
• the halogenated butyl rubber maybe produced either by treating finely divided butyl rubber with a halogenating agent such as chlorine or bromine, or by producing brominated butyl rubber by the intensive mixing, in a mixing apparatus, of brominating agents such as N-bromosuccinimide with a previously made butyl rubber.
• the halogenated butyl rubber may be produced by treating a solution or a dispersion in a suitable organic solvent of a previously made butyl rubber with corresponding brominating agents.
• the amount of halogenation during this procedure may be controlled so that the final terpolymer has the preferred amounts of halogen described hereinabove.
• the pressure under which the polymerizations take place is not important and may usually be in the range of from 0.01 to
• the compound of the general structure (I) may be prepared by admixture of [HC(CRR")(CRR'R”)] with MX 4 in the presence of R'X in a inert solvent, in which
• R is a group of the formula M'R'R 2 R 3
• R' is a group of the formula M'R R 5 R 6 ,
• R" is hydrogen, a Ci to C 12 alkyl, a C 6 to d aryl or a C 7 to C 20 alkylaryl, M is Zr or Hf, M' is Si, Ge, Sn or Pb, X is a halogen atom, and R 1 to R 6 is a d to C 12 alkyl group, a C 6 to C ⁇ 4 aryl or a C 7 to do alkylaryl.
• the R' is to be in ⁇ -position to the central carbon atom, as it is apparent from the above structure.
• inert solvent is not crucial, however, halogenalkanes, such as chloroalkanes, especially dichloromethane are preferred.
• the stabilization of the final compound with one or more R' is crucial for the preparation. To our knowledge, this is the very first isolated secondary-alkyl carbocation ever.
• said method of stabilizing a secondary-alkyl cation with a group of the general formula [M'R 4 R 5 R 6 ] + in which M' and R 4 to R 6 denote for the atoms/groups stated above is another subject of the present invention.
• Yet another subject of the present invention is a metalorganic compound comprising a non-coordinating anion of the general structure [M 2 X 9 ] " in which M is Zr or Hf and X is a halogen atom and a method of homo- or copolymerizing an olefin in the presence of a compound comprising an anion of the general structure [M 2 X 9 ] " in which M is Zr or Hf and X is a halogen atom.
• each R is independently hydrogen, a Ci to C 12 alkyl, a C 6 to C ⁇ aryl or a C to C 20 alkylaryl
• each E is independently B or Al
• E' and E" are independently Lewis acidic B and Al compounds, preferably EfCeFo): ?
• Z is a bridging group such as CN, N 3 , OCN, NH 2 , OH, OR, SR, NR 2 , PR 2 , and the like. Therefore compounds comprising a cation of the general structure (III)
• R' is a group of the formula M'R 4 R 5 R 6 ,
• R" is hydrogen, a d to d 2 alkyl, a C 6 to C ⁇ aryl or a C to do alkylaryl,
• M' is Si, Ge, Sn or Pb
• R 1 to R 6 is a Ci to C ⁇ 2 alkyl group, a C 6 to C ⁇ aryl or a C to do alkylaryl, is another obj ect of the invention.
• IP diene monomer isoprene
• Isobutylene (IB) was purified and dried by passing through columns of 10 wt% Na on Al 2 O 3 and appropriate mol-sieves and condensed directly into the reaction vessel.
• Solid state magic-angle spinning C NMR (relative to tetramethylsilane): ⁇ -1, 0, 3 (SiMe 3 , SnMe 3 ); 70 (CH); 217 (CH + ), 29 Si NMR: ⁇ 1 ppm.
• Fig. 1 shows the crystal structure of the cation in [CH ⁇ CH(SiMe 3 )(SnMe 3 ) ⁇ 2 ] + Hf 2 Cl ⁇ f , Fig.
• Example 5 The methodology of Example 5 was repeated, except that 3 mL of isoprene were added to the reaction mixture.
• Example 5 The methodology of Example 5 was repeated, except that 5 mL of isoprene were added to the reaction mixture.
• the product was poured into methanol (200 mL) to precipitate the polymer, stirred for 30 minutes then filtered, washing with methanol.
• the polymer was dried in an oven at 50°C to constant weight.
• the product was poured into methanol (200 mL) to precipitate the polymer, stirred for 30 minutes then filtered, washing with methanol.
• the polymer was dried in an oven at 50°C to constant weight. The yield of polyisoprene was 1.0 g.

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