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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0201—Oxygen-containing compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
  • B01J31/0235—Nitrogen containing compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
  • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
• • 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
  • C08F4/58—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 silicon, germanium, tin, lead, antimony, bismuth or compounds thereof

Definitions

• the present invention relates to novel cyclic organosilicon compounds and a method for using thereof as a component of catalysts for olefins polymerization.
• olefins polymerization or copolymerization in particular, in propylene polymerization or copolymerization, Ziegler-Natta catalyst systems comprising the cyclic organosilicon compounds as the external electron donor component exhibit dramatically-improved hydrogen response, and therefore can be used to prepare polymer having high melt-flowability and high isotacticity at high yield.
• Ziegler-Natta catalysts for olefins polymerization or copolymerization are well known in the art. These catalyst systems are typically composed of a transition metal-containing active component, generally comprising magnesium, titanium and halogen as main ingredients; and a co-catalyst component, usually an organo-aluminum compound.
• a transition metal-containing active component generally comprising magnesium, titanium and halogen as main ingredients
• a co-catalyst component usually an organo-aluminum compound.
• electron- donating compounds are widely used (1) as an internal electron donor in the solid Ziegler-Natta catalyst component and/or (2) as an external electron donor to be used in conjunction with the solid Ziegler-Natta catalyst component and the co-catalyst component.
• organo-silicon compounds are commonly used as external electron donors in the Ziegler-Natta catalyst system.
• external electron donors have silicon as the central atom containing at least one Si-OR, Si- OCOR, or Si-NR 2 bonds, where R is commonly an alkyl, alkenyl, or aryl group with 1 -20 carbon atoms.
• Si-OR Si-OR
• Si-OCOR Si-NR 2 bonds
• R is commonly an alkyl, alkenyl, or aryl group with 1 -20 carbon atoms.
• High MFR grade polypropylene is commonly achieved by adding peroxide to the polymer, but such obtained polypropylene usually has odor issues and reduced physical properties. So, production of reactor-grade high MFR polypropylene becomes necessary to avoid these issues.
• JP-A8-143620 proposes a method for propylene polymerization using a dialkoxysilane having two aliphatic amino substitutions as the external electron donor, but polymerization activity and polymer stereoregularity are not satisfactory when producing high MFR grade polypropylene.
• the present invention relates to novel cyclic organosilicon compounds and a method for using thereof as a component of catalysts for olefins polymerization.
• olefins polymerization or copolymerization in particular, in propylene polymerization or copolymerization, Ziegler-Natta catalyst systems comprising the cyclic organosilicon compounds as the external electron donor component exhibit dramatically-improved hydrogen response, and therefore can be used to prepare polymer having high melt-flowability and high isotacticity at high yield.
• the present invention relates to a catalyst system for the polymerization of co-polymerization of alpha-olefin comprising a solid Ziegler- Natta type catalyst component, a co-catalyst component, and an electron donor component comprising at least one cyclic organosilicon compound represented by the formula:
• R 1 is a hydrocarbon group with 1-20 carbon atoms; wherein R 2 is a bridging group with a backbone chain of 1-9 atoms, wherein the backbone of said bridging group is selected from the group consisting of aliphatic, alicyclic, and aromatic radicals; wherein R is a hydrocarbon group with 1-6 carbon atoms; wherein m is 0 or 1; and wherein R is an aliphatic, alicycylic, or aromatic group.
• the present invention also relates to a composition containing a compound of the cyclic organosilicon compounds of the aforementioned formula.
• the present invention also relates to a method of polymerizing an alpha-olefin comprising polymerizing the alpha-olefin in the presence of the cyclic organosilicon compound of the aforementioned formula.
• FIG. 1 is a plot showing the relationship between the amount of hydrogen used and the melt flow rate, in order to compare the hydrogen reactivity according to the species of the external donors, based on the results from examples 10-14 and comparative examples 1-5 in the present invention.
• the present invention relates to novel cyclic organosilicon compounds, a method for the preparation thereof and use thereof as a component of catalysts for olefins polymerization.
• olefins polymerization or copolymerization in particular, in propylene polymerization or copolymerization, it has been discovered that Ziegler-Natta catalyst systems comprising the cyclic organosilicon compounds of the present invention as the external electron donor component exhibit dramatically-improved hydrogen response, and therefore can be used to prepare polymer having high melt-flowability and high isotacticity at high yield.
• organosilicon compounds which are useful as electron donors in polymerization catalyst systems for the production of polyolefins, particularly polypropylene, are disclosed.
• the organosilicon compounds of the present invention may be used alone as single constituent in an electron donor component of the catalyst system or may be used in combination with one or more other compounds as an electron donor component of the catalyst system. If more than one compound is used as the electron donor component, one or more of the constituents may be organosilicon compounds of the present invention.
• organosilicon compounds of the present invention that may be used as electron donors in polymerization catalyst systems have a structure represented by the General Formula:
• R 1 is a hydrocarbon group with 1-20 carbon atoms.
• R z is a bridging group with a backbone chain of 1-9 atoms.
• "Backbone chain” in this context refers to the atoms that are in the direct linkage between N and O atoms. For example, if -CH 2 -CH 2 - is the bridging group, the backbone chain has two atoms, referring to the carbon atoms that provide the direct linkage between N and O atoms. Similarly, if the bridging group has the iso-structure, -CH(CH 3 )-CH 2 -, the associated backbone chain also has two atoms.
• the backbone of the bridging group is selected from the group consisting of aliphatic, alicyclic, and aromatic radicals.
• the backbone of the bridging group is selected from the group consisting of aliphatic radicals, with or without unsaturation.
• the bridging group may have one or more -C20 substituents (or side chains) extending off the backbone chain.
• the substituents may be branched or linear and may be saturated or unsaturated.
• the substituents may comprise aliphatic, alicyclic, and aromatic radicals.
• R is a hydrocarbon group with 1-6 carbon atoms.
• R 3 is a methyl or ethyl group.
• R 4 is an aliphatic, alicycylic, or aromatic group, which may have one or more C 1 -C 20 linear or branched, saturated or unsaturated substituents.
• the subscript m can be 0 or 1.
• One or more of carbon atoms and/or hydrogen atoms of R 1 , R 2 , R 3 , and R 4 , including any substituents thereof, may be replaced by a hetero-atom selected from the group consisting of N, O, S, Si, B, P, and halogen atoms.
• two or more of said R 1 , R 2 , R 3 , and R 4 may be linked to form one or more saturated or unsaturated ring structures.
• Suitable cyclic organosilicon compounds of the General Formula include, but not limited to:
• the present invention further relates to a process for olefin polymerization or copolymerization, wherein a cyclic organosilicon compound according to the invention is used as the external electron donor component in Zeigler-Natta catalyst systems.
• said process is homopolymerization or copolymerization of alpha olefins such as propylene.
• alpha olefins such as propylene
• Processes for the polymerization of alpha olefins such as propylene and application mode and amount of external electron donor compounds therein are well known in the art.
• Organosilicon compounds were characterized by 1H-NMR and GC-MS.
• Isotacticity of polymer was measured by heptane extraction method (heptane boiling extraction for 6 hours). Isotacticity is represented as heptane insoluable (HI), which is the ratio of the residual polymer weight after extraction to the initial polymer weight. 3. Melt flow rate (MFR) of polymer was measured according to ASTM D-1238, determined at 230°C, under the load of 2.16 kg.
• This example illustrates an organosilicon compound in accordance with the present invention and a method of preparing the same.
• This example illustrates another organosilicon compound in accordance with the present invention and a method of preparing the same.
• Example 1 The procedure and ingredients of Example 1 were followed except that 2-(tert- butylamino)ethanol (100 mmol) was replaced by 2-(tert-butylamino)-l-methyl-ethanol (100 mmol).
• This example illustrates another organosilicon compound in accordance with the present invention and a method of preparing the same.
• Example 1 The procedure and ingredients of Example 1 were followed except that 2-(tert- butylamino)ethanol (100 mmol) was replaced by 2-(tert-butylamino)-l-ethyl-ethanol (100 mmol).
• This example illustrates another organosilicon compound in accordance with the present invention and a method of preparing the same.
• Example 1 The procedure and ingredients of Example 1 were followed except that 2-(tert- butylamino)ethanol (100 mmol) was replaced by 2-piperidineethanol (100 mmol).
• This example illustrates another organosilicon compound in accordance with the present invention and a method of preparing the same.
• Example 1 The procedure and ingredients of Example 1 were followed except that 2-(tert- butylamino)ethanol (100 mmol) was replaced by 2-piperidineethanol (100 mmol) and tetraethyl orthosilicate (100 mmol) by tetramethyl orthosilicate (100 mmol).
• GC purity >99.0%; 1H-NMR (CDC13, 400 MHz) ⁇ (ppm): 4.0 (m, 2H), 3.5 (s, 6H), 3.2 (m, IH), 3.0 (m, IH), 2.6 (t, IH), 1.8 (m, 2H), 1.6 (m, 3H), 1.2 (m, 3H).
• This example illustrates another organosilicon compound in accordance with the present invention and a method of preparing the same.
• Example 1 The procedure and ingredients of Example 1 were followed except that 2-(tert- butylamino)ethanol (100 mmol) was replaced by 2-piperidineethanol (100 mmol) and tetraethyl orthosilicate (100 mmol) by isobutyltriethoxysilane (100 mmol).
• This example illustrates another organosilicon compound in accordance with the present invention and a method of preparing the same.
• Example 1 The procedure and ingredients of Example 1 were followed except that 2-(tert- butylamino)ethanol (100 mmol) was replaced by 2-piperidineethanol (100 mmol) and tetraethyl orthosilicate (100 mmol) by propyltriethoxysilane (100 mmol).
• This example illustrates another organosilicon compound in accordance with the present invention and a method of preparing the same.
• Example 1 The procedure and ingredients of Example 1 were followed except that 2-(tert- butylamino)ethanol (100 mmol) was replaced by 2-piperidineethanol (100 mmol) and tetraethyl orthosilicate (100 mmol) by ethyltriethoxysilane (100 mmol).
• GC purity >99.0%; 1H-NMR (CDC13, 400 MHz) ⁇ (ppm): 4.0 (m, 2H), 3.6 (m, 2H), 3.2 (t, 1H), 2.9 (m, 1H), 2.6 (m, 1H), 2.0-0.9 (m, 14H), 0.6 (m, 2H).
• This example illustrates another organosilicon compound in accordance with the present invention and a method of preparing the same.
• Example 1 The procedure and ingredients of Example 1 were followed except that 2-(tert- butylamino)ethanol (100 mmol) was replaced by 2-piperidineethanol (100 mmol) and tetraethyl orthosilicate (100 mmol) by methyltriethoxysilane (100 mmol).
• Examples 10-22 illustrate alpha olefin polymers in accordance with certain teachings of the present invention, and a method of preparing the same.
• a bench scale 2-liter reactor was used. The reactor was first preheated to 100°C with a nitrogen purge to remove residual moisture and oxygen. The reactor was thereafter cooled to 50°C.
• the reactor temperature was then raised to 70°C. Propylene was introduced to the reactor continually to keep the total reactor pressure at 90 psig. The polymerization was allowed to proceed for 1 hour. After completion of the polymerization reaction, the reactor was vented and cooled to 50°C. [0048] Then the reactor was opened and 500 mL of methanol added. The resulting mixture was stirred for 5 minutes followed by filtration to obtain the propylene homopolymer. The obtained polymer was dried at 80°C under vacuum for 6 hours.
• the polymerization activity per hour was estimated with the weight of the obtained polymer, and hexane insoluble (HI), melt flow rate (MFR) and molecular weight distribution (Mw/Mn) were measured.
• HI hexane insoluble
• MFR melt flow rate
• Mw/Mn molecular weight distribution
• a propylene polymer was prepared in the same manner as in Example 10 above, except that the amount of hydrogen was changed to 400 ml, 600 ml, 800 ml and 1000 ml, respectively.
• the results are represented in Table 1.
• a propylene polymer was prepared in the same manner as in Example 10 above, except that the following external electron donors:
• a propylene polymer was prepared in the same manner as in Example 10 above, except that 1.2 mmol of cyclohexylmethyldimethoxysilane (CHMDMS) was used as an external electron donor, instead of 1.2 mmol of hexahydro-l,l-dimethoxy-lH,3H-pyrido[l,2- c][l,3,2]oxazasiline in example 10.
• CHMDMS cyclohexylmethyldimethoxysilane
• a propylene polymer was prepared in the same manner as in Example 10 above, except that 1.2 mmol of cyclohexylmethyldimethoxysilane (CHMDMS) was used as an external electron donor, instead of 1.2 mmol of hexahydro-l,l-dimethoxy-lH,3H-pyrido[l,2- c][l,3,2]oxazasiline in example 10, and the amount of hydrogen used was changed to 400 ml, 600 ml, 800 ml and 1000 ml, respectively.
• CHMDMS cyclohexylmethyldimethoxysilane
• catalyst systems comprising the cyclic organosilicon compounds of the present invention as the external electron donor component exhibit dramatically-improved hydrogen response, and therefore a higher melt- flowability and higher isotacticity at high yield, as compared to catalyst systems utilizing CHMDMS as the electron donor.
• CHMDMS is well known in the art to demonstrate the highest hydrogen response of commonly used commercial electron donors
• the catalysts systems of the present invention achieves much higher MFR at the same lower hydrogen loading, or the same MFR as CHMDMS at a much lower hydrogen loading.

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