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
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
  • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
• • 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
• • 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
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• • 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
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/622—Component covered by group C08F4/62 with an organo-aluminium compound

Definitions

• the invention relates to a process for the preparation of a rubber-like copolymer of ethene, one or more ⁇ -olefins and optionally one or more polyunsaturated compounds under the influence of a catalyst system comprising a transition metal compound, the transition metal being chosen from groups 3-6 of the Periodic System of the Elements, an organometal compound and optionally a promoter.
• a process with such a catalyst system is already known from EP-A-44,119.
• amorphous ethene/ ⁇ -olefin copolymers also known as EAM rubbers
• amorphous ethene/ ⁇ -olefin/diene terpolymers also known as EADH rubbers
• Propene is often used as ⁇ -olefin, in which case EP or EPDM rubbers are obtained.
• the rubbers so obtained have a narrow molecular weight distribution (M D) and a narrow composition distribution. The latter means that nearly all the molecular chains have the same composition.
• M D molecular weight distribution
• the latter means that nearly all the molecular chains have the same composition.
• a narrow MWD is understood to mean an MWD of less than 5.
• Rubbers with a narrow MWD and a narrow composition distribution also have a number of drawbacks, however. The flow behaviour of such rubbers is poor and consequently they cannot be extruded or only with very poor results. Another drawback is the poor mixing behaviour of these rubbers in further processing; also see Noordermeer and Wilms, Kautschuk, Gummi & Kunststoffe, vol. 41(6), 1988, pp. 558-563.
• the object of the invention is to provide a process with which rubbers having a (very) wide MWD can be produced.
• This object is achieved in that the organometal compound in the catalyst system to be used in the process is an amido complex that answers the general formula
• the organometal compound (also referred to as 'co-catalyst') may be present in monomeric as well as in oligomeric form.
• the organometal compound (I) Due to the presence of the organometal compound (I) in the catalyst system, rubbers with a (very) wide MWD can be obtained. The rubbers consequently have excellent extrusion and mixing characteristics.
• the present patent application in all cases refers to a molecular weight distribution, because the molecular weight distribution can be determined easier and more univocally than the composition distribution. Actually, a widening of the distribution in general occurs, i.e. the composition distribution as well as the molecular weight distribution.
• the hydrocarbon group in each of the groups of formula (I) is understood to be an alkyl, aryl, acyl, cycloalkyl, cycloaryl or cycloacyl group. Hydrocarbon groups with one or more functional groups, such as halogen atoms, -OH, -OR, -COOH, -COOR or -NH 2 groups, may also be used.
• Me 1 preferably is aluminium.
• X 1 preferably is chlorine.
• the bridge that may be present between R 1 and R 2 may be a hydrocarbon group; silicon-, oxygen-containing groups are also possible.
• M in the MR 3 3 group preferably is Si.
• Each R 3 separately may be a hydrocarbon group having 1-20 C-atoms, as well as a group containing a hetero atom, the hetero atom having been chosen from groups 15, 16 or 17 of the Periodic System of the Elements, in particular from the group comprising N, 0, P and S or halogen.
• each R 3 separately may for instance also be an alkoxy, aryloxy, amine, amide group, an S compound, e.g.
• these aluminium amido complexes can be reacted with organoaluminium halogenides to give halogen-containing amido complexes of the general formula
• the catalyst system may contain an additional organometal compound of the following general formula:
• each R 4 separately represents hydrogen or a hydrocarbon group having 1-20 C- atoms
• X 2 is a halogen atom
• x ⁇ p represents the valency of Me 2 .
• aluminium is again chosen as Me 2 .
• X 2 preferably is chlorine.
• the most suitable compounds to be used as compound (II) are ethyl aluminium dichloride (MEAC) , sesqu ethyl aluminium chloride (SEAC) and/or diethyl aluminium chloride (DEAC).
• MEAC ethyl aluminium dichloride
• SEAC sesqu ethyl aluminium chloride
• DEAC diethyl aluminium chloride
• the catalyst system to be used in the process according to the invention also comprises a transition metal compound, the transition metal being chosen from groups 3-6 of the Periodic System of the Elements, such as scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum en chromium.
• the transition metal is chosen from group 5.
• vanadium is chosen as transition metal.
• suitable compounds are the halogenides, oxyhalogenides, the alkoxides and the acetyl acetonates, such as vanadium tetrachloride, vanadium oxytrichloride and vanadium acetylacetonate.
• Imidoaryl complexes of transition metals may also be used. Such complexes are described in EP-A-532,098. Preference is given to transition metal compounds that are soluble in the polymerization medium.
• a promoter enhances the activity of the catalyst system.
• the presence of a promoter also has an effect on the MWD. The higher the amount of promoter that is present, the narrower the MWD becomes.
• a promoter : transition metal molar ratio ⁇ 4 is applied.
• the promoter : transition metal molar ratio is ⁇ 2.
• Suitable promoters are halogenated compounds, such as trichloroacetic acid or esters thereof, hexachloroacetone, hexachloropropene, ⁇ -trichlorotoluene or perchlorocrotonic acid compounds. These compounds have a high chlorine content, however.
• the specific, low halogen content compounds suggested as promoter in EP-A- 44,119 may be used.
• these are compounds with not more than two halogen atoms per molecule. Examples of such compounds are the alkyl or alkoxyalkyl esters of phenyl , mono- or dihalogen acetic acid.
• the invention relates to a process in which a catalyst system according to the invention is used in the preparation of a rubber-like copolymer of ethene, one or more ⁇ -olefins and optionally one or more polyunsaturated compounds, e.g. in a liquid-phase polymerization reaction.
• a rubber-like copolymer is understood to be a copolymer which at room temperature and upwards has a crystallinity of at most 10%, measured by means of DSC (differential scanning calorimetry) .
• ⁇ -olefins suitable to be used as monomer besides ethene can be mentioned: propene, butene-1, pentene-1, hexene-1, octene-1 or the branched isomers of these, such as 4-methyl pentene-1, as well as styrene and ⁇ -methyl styrene. Mixtures of these alkenes can also be used; preference is given to propene and/or butene-1.
• Aliphatic polyunsaturated compounds in general contain 3 to 20 carbon atoms, the double bonds being either conjugated or, preferably, non-conjugated. Examples of such compounds are: 1,3-butadiene, isoprene, 2,3-dimethyl butadiene-1,3, 2-ethyl butadiene-1,3, piperylene, mycrene, allene, 1,2-butadiene, 1,4, 9-decatrienes, 1,4-hexadiene, 1,5-hexadiene and 4-methyl hexadiene-1,4.
• Alicyclic polyunsaturated compounds which may or may not comprise a bridge group, may be monocyclic as well as polycyclic.
• Examples of such compounds are norbornadiene and its alkyl derivatives; the alkylidene norbornenes, in particular the 5-alkylidene norbornenes-2 , in which the alkylidene group contains 1 to 20, preferably 1 to 8 carbon atoms; the alkenyl norbornenes, in particular the 5-alkenyl norbornenes-2 , in which the alkenyl group contains 2 to 20, preferably 2 to 10 carbon atoms, for instance vinyl norbornene, 5-(2 '-methyl-2 'butenyl )-norbornene-2 and 5-(3 '-methyl-2 'butenyl)-norbornene-2 ; dicyclopentadiene and the polyunsaturated compounds of bicyclo-(2,2 ,l)-heptane, bicyclo-(2,2,2)-octane, bicyclo-(3,2 ,l)-octane and bicyclo-(3,2,2)-nonane, at least one of the rings being
• compounds such as 4,7,8, 9-tetrahydroindene and isopropylidene tetrahydroindene may be used.
• dicyclopentadiene, vinyl norbornene, 5-methylene- or 5-ethylidene norbornene-2 or hexadiene-1,4 are applied. Mixtures of the compounds mentioned in the foregoing may also be used.
• the polyunsaturated compound may be present in the copolymer in quantities of up to 30 wt.%, preferably, however, up to 15 wt.%.
• an unsaturated compound with one or more functional groups such as halogen atoms, -OH, -OR, -COOH, -COOR or -NH 2 groups, may also be incorporated into the copolymer, in a quantity of up to 20 wt.%.
• the molar ratio of the polymers applied depends on the desired composition of the polymer. As the monomers have highly different polymerization rates, it is not possible to give generally applicable molar ratio ranges. However, for the copolymerization of ethene and propene a molar ratio between 1 : 1 and 1 : 50 will generally be chosen. If a polyunsaturated compound is copolymerized, its molar ratio relative to ethene will mostly be between 0.0001 : 1 and 1 : 1.
• the polymerization reaction is usually carried out at a temperature between -40° and 200°C, preferably between 10° and 80°C.
• the pressure will usually be 0.1-5 MPa, but it is also possible to operate at higher or lower pressures.
• the process is preferably carried out continuously, but it can also be carried out semi- continuously or batchwise.
• the residence time involved may vary from a few seconds to a few hours. In general a residence time between a few minutes and one hour will be chosen. Variation of the residence time in the reactor also provides a way to control the MWD. The longer the residence time, the wider the MWD.
• the polymerization may take place in a liquid which is inert in respect of the catalyst system, for instance one or more saturated aliphatic hydrocarbons, such as butane, pentane, hexane, heptane, pentamethyl heptane or petroleum fractions; aromatic hydrocarbons, for instance benzene or toluene, or halogenated aliphatic or aromatic hydrocarbons, for instance tetrachloroethylene. It is possible to operate at such a temperature and pressure that one or more of the monomers applied, in particular the ⁇ -olefin, for instance propene, is liquid and is present in such a large quantity that it serves as 5 dispersing agent. An additional dispersing agent will not be needed then.
• saturated aliphatic hydrocarbons such as butane, pentane, hexane, heptane, pentamethyl heptane or petroleum fractions
• aromatic hydrocarbons for instance benzene or toluene
• the process according to the invention may be carried out in a polymerization reactor filled with gas and liquid, as well as in a reactor completely filled with liquid.
• a completely or partially heterogenized 0 catalyst system makes it possible to carry out the polymerization process in suspension or in the gas phase.
• the molecular weight can moreover be set, in addition to the possibilities already mentioned, by means of techniques known to the person skilled in the art. In 5 particular, this may be effected through application of chain length regulators, such as diethyl zinc and, preferably, hydrogen. Very small amounts of hydrogen already influence the molecular weight to a sufficient degree. 0 Surprisingly, it has been found that the catalyst system described in the foregoing is highly suitable to be used in liquid-phase processes at room temperature or even higher temperatures, so that, in contrast to the conventional liquid-phase processes, the 5 heat of reaction can be removed more efficiently. This can be effected, as is known, by strong cooling of the feed to the reactor, as well as by evaporating part of the reaction medium. Upon completion of the polymerization the polymer can be worked up in several ways. Evaporation of
• the solvent as well as steam coagulation are suitable for this purpose in the case of liquid-phase processes.
• copolymers produced by the process according to the invention generally contain between 25 and 85 wt.% of ethene. However, preference is given to products with
• the main advantage of the use of a catalyst system according to the invention is that rubbers with a very wide MWD, larger than 5 and even >20 higher can be obtained (in a single reactor). It has been found moreover that if compound (II) and/or the promoter (as well) is/are present, the MWD is infinitely adjustable, i.e. each MWD can be obtained.
• Such copolymers are suitable for many applications, e.g. for the manufacture of hoses, cables, conveyor belts, sealing profiles. Optionally, they can be vulcanized by the customary methods with utilization of substances yielding free radicals, such as peroxides, or with sulphur.
• copolymers have excellent processing properties.
• the customary techniques used to make a rubber processable can also be applied to these copolymers.
• the polymer can be blended with oil; this is preferably done after the polymerization.
• agents can be added which make it possible to obtain friable bales. This can be achieved for instance by adding talcum or another substance or by making use of a system as described in EP-A-427.339.
• the composition described in EP-A-427.339, comprising a thickening agent and an anionic dispersion agent, has been found to be very suitable for the products according to the invention.
• the invention will be elucidated by means of the following, non-restrictive examples and comparative experiments.
• FT-IR Fourier transformation infrared spectroscopy
• the composition of the copolymer was determined in accordance with the method that is customary in the rubber industry.
• the FT-IR measurement gives the composition of the copolymer in monomer unit weight percentages.
• the composition of the copolymer determined with FT-IR is expressed in weight percentages of propene units (%C 3 ) in the examples.
• the molecular weight was determined using size exclusion chromatography- differential viscosimetry (SEC-DV).
• DSC differential scanning calorimetry
• the Mooney M L (l+4) of the copolymer is determined in accordance with ISO 289 at a temperature of 125°C.
• the yield of polymer in the examples is expressed in g of copolymer per mmol of transition metal.
• the abbreviation 'nd' in the tables means 'not determined' .
• Al-amidos were prepared by reacting triethyl aluminium (TEA) with an amine. In this reaction a gas (ethane) was released. The reaction took place at room temperature (in the case of aromatic amines) and at approx. 80°C (in the case of aliphatic amines). The reaction yielded diethyl aluminium amido (DEAN). By mixing one equivalent of DEAN with one equivalent of monoethyl aluminium dichloride the Al-amido (SEAC-N), Et 1#5 Al 1 Cl 1 (NR 1 R 2 ) 0 , s , was formed.
• a glass 1.5-litre autoclave was filled with 300 ml of (special boiling point) gasoline and compound I and, optionally, compound II.
• the reactor was pressurized to 0.8 MPa with purified monomers and so conditioned that the propene : ethene ratio in the gas cap was 2:1.
• the temperature of the reactor was about 30°C.
• the transition metal compound and, optionally, the promoter were dosed to the reactor by means of a pump.
• the monomer concentrations were kept as constant as possible by supplying propene (200 Nl/h) and ethene (100 Nl/h) to the reactor.
• propene 200 Nl/h
• ethene 100 Nl/h
• the reactor was depressurized, the solution was collected and dried. In each case an amorphous copolymer of ethene and propene was obtained.
• Example 1 is the blank example.
• the transition metal compound used was vanadium trichloride (V0C1 3 ) (50 ⁇ mol).
• the Al-amido (compound I) was used in a quantity of 150 ⁇ mol.
• Compound II was sesquiethyl aluminium chloride (SEAC), 150 ⁇ mol.
• Al-amido (Ethyl) 1#5 A1(Cl) (amido) 0 . 5 (SEAC-N).
• Table 1 contains examples of aliphatic, aromatic, sterically small and large amines, amines with hetero atoms at the nitrogen, and of chelating amines (i.e. amines containing an additional functional group) .

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=19864895

Family Applications (1)

Country Status (9)

Cited By (5)

Citations (7)

• 1994
  • 1994-11-14 NL NL9401893A patent/NL9401893A/nl not_active Application Discontinuation
• 1995
  • 1995-10-31 EP EP95936797A patent/EP0792296B1/en not_active Expired - Lifetime
  • 1995-10-31 CA CA002205304A patent/CA2205304A1/en not_active Abandoned
  • 1995-10-31 CN CN95197277A patent/CN1171795A/zh active Pending
  • 1995-10-31 WO PCT/NL1995/000376 patent/WO1996015161A1/en not_active Application Discontinuation
  • 1995-10-31 BR BR9510333A patent/BR9510333A/pt not_active Application Discontinuation
  • 1995-10-31 DE DE69510366T patent/DE69510366T2/de not_active Expired - Fee Related
  • 1995-10-31 AU AU38573/95A patent/AU3857395A/en not_active Abandoned
• 1997
  • 1997-05-15 KR KR1019970703370A patent/KR970707180A/ko not_active Application Discontinuation

Patent Citations (7)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events