WO2022228260A1 - 丙烯基共聚物、其制备方法和用途和包含其的聚丙烯组合物 - Google Patents

丙烯基共聚物、其制备方法和用途和包含其的聚丙烯组合物 Download PDF

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WO2022228260A1
WO2022228260A1 PCT/CN2022/088102 CN2022088102W WO2022228260A1 WO 2022228260 A1 WO2022228260 A1 WO 2022228260A1 CN 2022088102 W CN2022088102 W CN 2022088102W WO 2022228260 A1 WO2022228260 A1 WO 2022228260A1
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Prior art keywords
propylene
based copolymer
polypropylene
polymerization
catalyst
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PCT/CN2022/088102
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English (en)
French (fr)
Chinese (zh)
Inventor
宋文波
方园园
韩书亮
金钊
王路生
吕静兰
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Priority claimed from CN202110449881.5A external-priority patent/CN115232236B/zh
Priority claimed from CN202110448666.3A external-priority patent/CN115232235B/zh
Priority claimed from CN202110449898.0A external-priority patent/CN115246967B/zh
Priority to KR1020237040682A priority Critical patent/KR20230175305A/ko
Priority to US18/556,888 priority patent/US20240218098A1/en
Priority to EP22794731.4A priority patent/EP4332132A4/en
Priority to CN202280030647.1A priority patent/CN117321095A/zh
Priority to JP2023565395A priority patent/JP2024514968A/ja
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CA3216518A priority patent/CA3216518A1/en
Priority to BR112023022186A priority patent/BR112023022186A2/pt
Publication of WO2022228260A1 publication Critical patent/WO2022228260A1/zh
Anticipated expiration legal-status Critical
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    • 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
    • C08F210/06—Propene
    • 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
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • 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
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • 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
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/27—Amount of comonomer in wt% or mol%
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

Definitions

  • the present invention belongs to the field of olefin polymerization.
  • the present invention relates to a propylene-based copolymer, a method for preparing the propylene-based copolymer, the use of the propylene-based copolymer, and a polypropylene composition comprising the propylene-based copolymer.
  • Propylene-based copolymers are one of the most widely used polyolefin materials. Propylene- ⁇ -olefin copolymers with high comonomer content are characterized by high elasticity and can be used as thermoplastic elastomers for impact modification of polypropylene materials. However, as the comonomer content increases, especially when the comonomer content reaches more than 10 wt%, the compatibility of the propylene-based copolymer with polypropylene decreases. The incorporation of propylene-based copolymers will hinder the crystallization of polypropylene materials, thereby affecting the mechanical properties of the materials.
  • propylene-alpha-olefin copolymers that promote crystallization of polypropylene when incorporated into polypropylene to form a blend material. Crystallization of propylene-alpha-olefin copolymers is generally related to the degree of dispersion of the comonomers in the propylene segments.
  • Propylene- ⁇ -olefin copolymers with high comonomer content have the characteristics of high elasticity and low glass transition temperature, and can be used in low temperature environment. However, due to its slow crystallization and high viscosity, it may cause problems of sticking and agglomeration of pellets during storage and transportation. Propylene copolymers with high comonomer content generally have lower onset melting temperatures, which lead to more severe problems of blocking and caking during storage and transport in high temperature regions, especially in summer. Therefore, there is also an urgent need in the art to develop a propylene-based polymer with high comonomer content and high initial melting temperature to solve the problems of blocking and caking during storage and transportation.
  • chiral bis-indenyl metallocene catalysts can be used to prepare highly crystalline isotactic polypropylene and its copolymers.
  • WO2002/01745, US2002/0004575A1, WO2002/083753A1 and US6525157 disclose the preparation of propylene/ethylene copolymers containing tacticity within the propylene sequence using chiral metallocene rac-Me2Si(1-indenyl)2HfMe2.
  • US6057408 discloses a process for the preparation of high molecular weight propylene/ethylene copolymers with high crystallinity in the propylene sequence using chiral bis-indenyl metallocenes.
  • the object of the present invention is to provide a propylene-based copolymer, its preparation method and use, and a polypropylene composition comprising the propylene-based copolymer.
  • the number of monodisperse comonomer structural units in the base copolymer, the monodisperse comonomer structural unit is a comonomer structural unit in the form of a single comonomer structural unit inserted
  • a second aspect of the present invention provides a method for preparing the above-mentioned propylene-based copolymer, the method comprising:
  • step (B) The ionic catalyst homogeneous solution obtained in step (A) is fed into the polymerization reactor through the pipeline connected to the polymerization reactor, and mixed with propylene monomer, one or more comonomers, Optional hydrogen contact, olefin polymerization, yields the propylene-based copolymer.
  • the main catalyst is a metallocene catalyst, preferably at least one selected from the compounds represented by formula (I);
  • M is a metal selected from titanium, hafnium or zirconium; G is carbon, silicon, germanium, tin or lead; each R and R' is independently selected from hydrogen, substituted or unsubstituted C 1 -C 20 hydrocarbyl; each R" is independently selected from hydrogen atoms, halogen atoms, C 1 -C 20 hydrocarbyl, C 1 -C 20 alkoxy or C 6 -C 20 aryloxy groups, these groups is straight-chain, branched or cyclic and optionally replaced by a halogen atom, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, C 6 -C 10 aryl or C 6 -C 10 aryloxy each R"' is independently selected from a hydrogen atom, a C 1 -C 20 hydrocarbyl, a C 1 -C 20 alkoxy group, or a C 6 -C 20 aryloxy group; and/or
  • the cocatalyst is a boron-containing compound cocatalyst, aluminoxane cocatalyst or a combination thereof.
  • a third aspect of the present invention provides a polymer composition comprising the propylene-based copolymer of the present invention; preferably the polymer composition comprises the propylene-based copolymer of the present invention and at least one further polymer; more preferably The polymer composition comprises polypropylene and a propylene-based copolymer of the present invention, wherein the polypropylene comprises a polypropylene homopolymer, a polypropylene copolymer different from the propylene-based copolymer of the present invention, or a combination thereof.
  • a fourth aspect of the present invention provides the use of the propylene-based copolymer of the present invention in preparing a polypropylene composition comprising polypropylene and the propylene-based copolymer.
  • the propylene-based copolymers of the present invention have a relatively high comonomer content with a particularly selected degree of comonomer dispersion.
  • the present application has surprisingly found that, by selecting a specific range of comonomer dispersion, propylene-based copolymers with advantageous properties can be obtained.
  • the propylene-based copolymer of the present invention has excellent compatibility with polypropylene, can promote the crystallization of polypropylene and can improve the mechanical properties of the obtained polypropylene material.
  • the manufacturing method of the propylene-based copolymer of the present invention can form an ionic catalyst homogeneous solution in-situ in the pipeline, so that the catalyst system has excellent polymerization activity (especially at higher temperature, such as 80°C or higher temperature) and comonomer selectivity, which in turn can result in olefin polymers having higher comonomer content and relatively low, particularly advantageous comonomer dispersion.
  • the present invention enables the catalyst to form active sites in situ in the pipeline and inject it into the polymerization reactor as a homogeneous aliphatic solution, which has significant operational advantages.
  • references to “one embodiment” or “some embodiments” means that a feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment.
  • the features, structures or characteristics can be combined in any suitable manner in one or more embodiments.
  • ranges include, but are not limited to, content ranges, numerical ranges, weight ratio ranges, molar ratio ranges, and the like.
  • applicants' intention is to individually disclose or claim every possible range and value that the range can reasonably include, including the endpoints of the range, the point values within the range and any sub-ranges and combinations of sub-ranges subsumed therein.
  • the scope of the present application may specifically include any combination of any endpoint and any point value of the stated range.
  • "about” can comprise less than or equal to 5%, optionally less than or equal to 4%, optionally less than or equal to 3%, optionally less than or equal to 2%, optionally less than or equal to 1%, optionally less than or equal to A variation of 0.5% and optionally less than or equal to 0.1% in certain aspects.
  • Figure A1 shows the dynamic mechanical curves of the polypropylene material before and after incorporating the propylene-based copolymer of Example A4 of the present invention.
  • Figure A2 shows the dynamic mechanical curves of the polypropylene material before and after incorporating the propylene-based copolymer of Example A6 of the present invention.
  • Figure A3 shows the crystallization temperatures (determined by DSC testing) of polypropylene compositions incorporating the propylene-based copolymers of Examples A1-A4 with different ethylene contents and incorporating the propylene-based copolymers of Comparative Examples B2 and B3.
  • Figures C1-C3 show the DSC curves of the polypropylene compositions prepared in Examples C1-C3, respectively.
  • Figure D shows the dynamic mechanical curves of the homopolypropylene material before and after incorporating the propylene-based copolymer of Comparative Example B1.
  • the present invention provides a propylene-based copolymer comprising structural units derived from propylene and structural units derived from comonomers, preferably 60-95 wt% of structural units derived from propylene and 5-40 wt% of structural units derived from propylene Structural units derived from comonomers; more preferably, the propylene-based copolymer comprises 75-93 wt % of structural units derived from propylene and 7-25 wt % of structural units derived from comonomers; the comonomer is ethylene and at least one of C 4 -C 20 ⁇ -olefins; in the propylene-based copolymer, the comonomer dispersion D [PCP]/[C] is between 50% and 70%, preferably 60% ⁇ 70%, such as 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%
  • the comonomer dispersion degree D [PCP]/[C] [PCP]/[C] ⁇ 100%, wherein [PCP] is the number of monodisperse comonomer structural units in the propylene-based copolymer, and the The monodisperse comonomer structural unit is a comonomer structural unit in the form of a single comonomer structural unit inserted into a propylene segment, and [C] is the total number of comonomer structural units in the propylene-based copolymer.
  • the weight percent of the propylene-derived structural unit and the comonomer-derived structural unit of the propylene-based copolymer is the weight percent based on the total weight of the propylene-based copolymer.
  • the "comonomer dispersion degree” in the present invention represents the degree of dispersion of the comonomer in the propylene segment.
  • PCP stands for monodisperse comonomer structural unit, which refers to a comonomer structural unit in the form of a propylene monomer structural unit (P) - a single comonomer structural unit (C) - a propylene monomer structural unit (P)
  • [ PCP] represents the number of such structural units, the ratio of which to the total number of comonomer structural units is the comonomer dispersity D [PCP]/[C] .
  • the total content of comonomer structural units [C] and the content of monodisperse comonomer structural units [PCP] can be obtained by 13 C NMR.
  • the "amount" of [PCP] and [C] may be measured in the same unit, for example, both are molar amount (molar content), or both are weight (weight content).
  • the comonomer dispersion D [PCP]/[C] can be measured by 13 C NMR.
  • 13 C NMR spectroscopy is a method known in the art for measuring the amount of comonomer incorporated into a polymer and how the comonomer structural units are incorporated in the polymer chain. See, eg, Journal of Macromolecular Science, Reviews in Macromolecular Chemistry and Physcis, C29(2&3), 201-317 (1989).
  • the basic procedure for determining the comonomer content of an olefin copolymer consists in obtaining a 13 C NMR spectrum under conditions where the intensities of the peaks corresponding to different carbons in the sample are directly proportional to the total number of contributing nuclei in the sample. Methods to ensure this proportionality are known in the art and include allowing sufficient relaxation time after pulses, using gated decoupling techniques, using relaxants, and the like. After obtaining the13C NMR spectrum and integrating the peaks, the peaks associated with the monomer building blocks were assigned. Such assignments are known in the art, for example, by reference to known spectra or literature, or by synthesis and analysis of model compounds, or by the use of isotopically labeled monomers. The degree of comonomer dispersion can be determined by the ratio of the peak integrals corresponding to monodisperse comonomer structural units to the peak integrals corresponding to all comonomer structural units in the copolymer.
  • the propylene-based polymers of the present invention have a high comonomer content.
  • "High comonomer content” as used herein refers to a comonomer content of 5 wt% or more, based on the total weight of the propylene-based copolymer.
  • the comonomer content may be 5 wt % to 40 wt %, preferably 7 wt % to 25 wt %, more preferably 10 wt % to 25 wt %.
  • the comonomer content may be, for example, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt% , 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%, 31wt%, 32wt%, 33wt%, 34wt% %, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%.
  • the comonomers are preferably ethylene, 1-butene and/or 1-hexene. In the most preferred embodiment, the comonomer is ethylene.
  • the propylene-based copolymer of the present invention is a propylene-ethylene copolymer.
  • the ethylene monomer dispersity D [PEP]/[E] is between 50% and 70%, preferably between 60% and 70%; for example, 50%, 51%, 52% %, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%.
  • the ethylene monomer dispersion degree D [PEP]/[E] [PEP]/[E] ⁇ 100%, wherein, [PEP] is the number of monodisperse ethylene monomer structural units in the propylene-ethylene copolymer, so The monodisperse ethylene monomer structural unit is an ethylene monomer structural unit in the form of a single ethylene monomer structural unit inserted into a propylene segment, and [E] is the total number of ethylene monomer structural units in the propylene-ethylene copolymer.
  • the ratio of triad ethylene monomer units [EEE]/[E] is in the range of 3.5-5%; and/or diad ethylene monomer units The range of the ratio [EE]/[E] is 15-20%.
  • the propylene-based copolymer consists essentially of propylene monomeric structural units and ethylene monomeric structural units, or consists of propylene monomeric structural units and ethylene monomeric structural units.
  • the triad tacticity (mmm tacticity) of the propylene-based copolymer of the present invention is measured by 13 C NMR, which is carried out on a nuclear magnetic resonance apparatus such as Bruker-300 with deuterated chloroform as a solvent at 110° C. Test; see specifically the method in US Pat. No. 7,232,871.
  • the mmm tacticity of the propylene-based copolymer of the present invention preferably ranges between 75% and 99%, more preferably between 80% and 97%.
  • the tacticity index m/r of the propylene-based copolymers of the present invention is measured by 13 C NMR, as described by HNCheng in Macromolecules, Vol. 17, pp. 1950-1955 (1984).
  • m and r describe the stereochemistry of adjacent pairs of propylene monomer building blocks, with m being meso and r being racemic.
  • An m/r of 1 generally describes a syndiotactic polymer, while an m/r of 2 describes an atactic material.
  • the m/r of the propylene-based copolymer of the present invention is preferably 3 to 15.
  • the density of the propylene-based copolymer of the present invention is preferably 0.84 to 0.92 g/cc, more preferably 0.85 to 0.89 g/cc.
  • the density is measured at room temperature by the ASTM D-1505 test method.
  • room temperature refers to about 25°C.
  • the melt flow rate (MFR) of the propylene-based copolymer of the present invention at 190° C. under a load of 2.16kg may be lower than or equal to 100g/10min, preferably lower than or equal to 20g/10min, and greater than 0.5g/10min; Measured by ASTM D-1238 test method.
  • the propylene-based copolymer of the present invention has a melt index of 0.5 to 50 g/10 min (190° C.; 2.16 kg).
  • the propylene-based copolymer of the present invention When the propylene-based copolymer of the present invention is blended with polypropylene, it can promote the crystallization of polypropylene.
  • the polypropylene includes polypropylene homopolymers, polypropylene copolymers other than the propylene-based copolymers of the present invention, or combinations thereof.
  • the polypropylene copolymer different from the propylene-based copolymer of the present invention contains 95 to 100 wt % of structural units derived from propylene and 0 to 5 wt % of structural units derived from comonomers; wherein the optional comonomers are each At least one selected from the group consisting of ethylene and C 4 -C 20 alpha-olefins.
  • the propylene-based copolymer can act as a polypropylene crystallization accelerator.
  • the propylene-based copolymer of the present invention can improve the mechanical properties of polypropylene materials, and therefore, the propylene-based copolymers can also be used as modifiers for polypropylene materials, for example, as modifiers for mechanical properties of polypropylene materials.
  • the propylene-based copolymer of the present invention has good compatibility with polypropylene materials.
  • the material obtained by blending the propylene-based copolymer of the present invention with the polypropylene material has only one glass transition temperature; and the crystallization temperature Tc (obtained by DSC test) of the material obtained after blending increases, indicating that the propylene-based copolymer of the present invention is The incorporation of the compound can promote the crystallization of polypropylene.
  • the present invention provides a method for preparing a propylene-based copolymer, preferably the propylene-based copolymer of the present invention, the method comprising:
  • step (B) The ionic catalyst homogeneous solution obtained in step (A) is fed into the polymerization reactor through the pipeline connected to the polymerization reactor, and mixed with propylene monomer, one or more comonomers, Optional hydrogen contact, olefin polymerization, yields the propylene-based copolymer.
  • the procatalyst used in the process of the present invention is a metallocene catalyst.
  • the metallocene catalysts are known in the art.
  • the main catalyst is at least one selected from the compounds represented by formula (I);
  • M is a metal selected from titanium, hafnium or zirconium; G is carbon, silicon, germanium, tin or lead; each R and R' is independently selected from hydrogen, substituted or unsubstituted C 1 -C 20 hydrocarbyl; each R" is independently selected from hydrogen atoms, halogen atoms, C 1 -C 20 hydrocarbyl, C 1 -C 20 alkoxy or C 6 -C 20 aryloxy groups, these groups is straight-chain, branched or cyclic and optionally replaced by a halogen atom, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, C 6 -C 10 aryl or C 6 -C 10 aryloxy each R"' is independently selected from a hydrogen atom, a C 1 -C 20 hydrocarbon group, a C 1 -C 20 alkoxy group, or a C 6 -C 20 aryloxy group;
  • each R and R' is independently selected from hydrogen, substituted or unsubstituted C 1 -C 20 alkyl; each R" is independently selected from hydrogen atom, halogen atom, C 1 -C 12 alkane radicals, C 1 -C 12 alkoxy groups or C 6 -C 12 aryloxy groups, which are straight-chain, branched or cyclic and optionally surrounded by halogen atoms, C 1 -C 10 alkyl groups , C 1 -C 10 alkoxy, C 6 -C 10 aryl or C 6 -C 10 aryloxy further substituted; each R"' is independently selected from hydrogen atom, C 1 -C 12 alkyl, C 1 -C 12 alkoxy or C 6 -C 12 aryloxy groups;
  • each R and R' is independently selected from hydrogen, substituted or unsubstituted C 1 -C 12 alkyl; each R " is independently selected from hydrogen atom, halogen atom, C 1 -C 6 Alkyl, C 1 -C 6 alkoxy or C 6 -C 12 aryloxy groups, which are straight-chain, branched or cyclic and optionally surrounded by halogen atoms, C 1 -C 6 alkanes group, C 1 -C 6 alkoxy group, C 6 -C 10 aryl group or C 6 -C 10 aryloxy group is further substituted; each R"' is independently selected from hydrogen atom, C 1 -C 6 alkyl group , C 1 -C 6 alkoxy or C 6 -C 12 aryloxy group;
  • each R and R' is independently selected from methyl, ethyl, propyl, butyl, pentyl or hexyl; each R" is independently selected from hydrogen atom, halogen atom, C 1 - C 3 alkyl, C 1 -C 3 alkoxy or C 6 -C 8 aryloxy groups, which are straight-chain, branched or cyclic and optionally surrounded by halogen atoms, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 6 -C 8 aryl or C 6 -C 8 aryloxy further substituted; each R"' is independently selected from hydrogen, C 1 -C 3 an alkyl, C 1 -C 3 alkoxy or C 6 -C 8 aryloxy group;
  • each R and R' is independently selected from methyl, isopropyl or tert-butyl; each R" is independently selected from hydrogen atom, halogen atom, methyl, ethyl or propyl ; each R"' is independently selected from a hydrogen atom, methyl, ethyl or propyl.
  • the M is preferably a metal selected from hafnium and zirconium.
  • the G is preferably silicon.
  • the halogen atom is preferably selected from fluorine, chlorine, bromine, iodine, or a combination thereof, more preferably chlorine.
  • the cocatalyst is a boron-containing compound-based cocatalyst or an aluminoxane-based cocatalyst.
  • the cocatalyst is a boron-containing compound cocatalyst.
  • the boron-containing compound-based cocatalyst comprises a structure represented by formula (II);
  • Z is an optionally substituted phenyl derivative, wherein the optional substituent is a C 1 -C 6 haloalkyl group or a halogen group.
  • the boron-containing compound-based cocatalyst comprising the structure represented by formula (II) is known in the art.
  • the boron-containing compound cocatalyst is selected from triphenylcarbonium tetrakis(pentafluorophenyl) boron compound, N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl) borate, N , one or more of N-dimethylbenzylammonium tetrakis (pentafluorophenyl) borate and N,N-dimethylanilinium tetrakis (pentafluorophenyl) borate.
  • the cocatalyst may be an aluminoxane-based cocatalyst, such as an alkylaluminoxane-based cocatalyst, such as methylaluminoxane, and the like.
  • the aluminoxane-based cocatalyst is preferably a modified alkyl aluminoxane-based cocatalyst soluble in an alkane solvent, such as a modified methylaluminoxane (such as Nouryon MMAO-3A and MMAO-7, or Customized products soluble in alkane solvents such as hexane and heptane).
  • precontacting the main catalyst with the cocatalyst can be flexible.
  • the pre-contacting of the main catalyst and the co-catalyst is in the form of mixing the main catalyst mixed solution with the co-catalyst mixed solution, wherein the main catalyst mixed solution is a mixture of the main catalyst and the solvent, and the co-catalyst is mixed
  • the liquid is a mixture of the cocatalyst and the solvent, that is, the main catalyst and the cocatalyst are mixed with the solvent first, and then mixed together, for example, at a preset flow rate.
  • the "in-situ formation of a homogeneous solution of the ionic catalyst in the pipeline connected to the polymerization reactor” means that the mixed solution of the main catalyst and the mixed solution of the co-catalyst can be directly combined on the pipeline, and the mixed solution of the main catalyst and the co-catalyst can be directly combined on the pipeline.
  • the ionic catalyst is formed in the pipeline and then enters the polymerization reactor to initiate the reaction.
  • one or both of the main catalyst mixture and the cocatalyst mixture may be mixed via a mixer and then sent to the pipeline.
  • the main catalyst mixed solution and the cocatalyst mixed solution are directly combined on the pipeline to form an ionic catalyst in the pipeline leading to the polymerization reactor, and then enter the polymerization reactor to initiate the reaction.
  • the homogeneous solution of the ionic catalyst formed in situ in the pipeline means that the solution observed with the naked eye is homogeneous, with no obvious particle precipitation or no particle precipitation, and no solid particle sedimentation after standing for 30 minutes.
  • the length L of the pipeline that the main catalyst and the co-catalyst pass through from the beginning of the pre-contact to entering the polymerization reactor should be controlled to satisfy the following formula: 30 ⁇ W/d 2 ⁇ L ⁇ 1000 ⁇ W/d 2 , where L is in m, and W is the total flow of the main catalyst, co-catalyst and solvent (usually the sum of the flow of the main catalyst mixed solution and the co-catalyst mixed solution) , the unit is kg/h, d is the inner diameter (diameter) of the pipeline, and the unit is mm.
  • L satisfies the following formulas: 30 ⁇ W/d 2 ⁇ L ⁇ 900 ⁇ W/d 2 ; 30 ⁇ W/d 2 ⁇ L ⁇ 850 ⁇ W/d 2 ; 30 ⁇ W/ d 2 ⁇ L ⁇ 800 ⁇ W/d 2 ; 30 ⁇ W/d 2 ⁇ L ⁇ 750 ⁇ W/d 2 ; 30 ⁇ W/d 2 ⁇ L ⁇ 700 ⁇ W/d 2 ; 30 ⁇ W/d 2 ⁇ L ⁇ 650 ⁇ W/d 2 ; 30 ⁇ W/d 2 ⁇ L ⁇ 600 ⁇ W/d 2 ; 30 ⁇ W/d 2 ⁇ L ⁇ 550 ⁇ W/d 2 ; 30 ⁇ W/d 2 ⁇ L ⁇ 500 ⁇ W/d 2 ; 30 ⁇ W/d 2 ⁇ L ⁇ 450 ⁇ W/d 2 ; 30 ⁇ W/d 2 ⁇ L ⁇ 400 ⁇ W/d 2 ; 30 ⁇ W/d 2 ⁇ L ⁇ 350 ⁇ W/d 2 ; 30 ⁇ W/d 2 ⁇ L ⁇ 300 ⁇ W/d 2
  • L satisfies the following formulas: 40 ⁇ W/d 2 ⁇ L ⁇ 1000 ⁇ W/d 2 ; 40 ⁇ W/d 2 ⁇ L ⁇ 900 ⁇ W/d 2 ; 40 ⁇ W/ d 2 ⁇ L ⁇ 850 ⁇ W/d 2 ; 40 ⁇ W/d 2 ⁇ L ⁇ 800 ⁇ W/d 2 ; 40 ⁇ W/d 2 ⁇ L ⁇ 750 ⁇ W/d 2 ; 40 ⁇ W/d 2 ⁇ L ⁇ 700 ⁇ W/d 2 ; 40 ⁇ W/d 2 ⁇ L ⁇ 650 ⁇ W/d 2 ; 40 ⁇ W/d 2 ⁇ L ⁇ 600 ⁇ W/d 2 ; 40 ⁇ W/d 2 ⁇ L ⁇ 550 ⁇ W/d 2 ; 40 ⁇ W/d 2 ⁇ L ⁇ 500 ⁇ W/d 2 ; 40 ⁇ W/d 2 ⁇ L ⁇ 450 ⁇ W/d 2 ; 40 ⁇ W/d 2 ⁇ L ⁇ 400 ⁇ W/d 2 ; 40 ⁇ W/d 2 ⁇ L ⁇ 350 ⁇ W/d 2
  • L satisfies the following formulas: 50 ⁇ W/d 2 ⁇ L ⁇ 1000 ⁇ W/d 2 ; 50 ⁇ W/d 2 ⁇ L ⁇ 900 ⁇ W/d 2 ; 50 ⁇ W/ d 2 ⁇ L ⁇ 850 ⁇ W/d 2 ; 50 ⁇ W/d 2 ⁇ L ⁇ 800 ⁇ W/d 2 ; 50 ⁇ W/d 2 ⁇ L ⁇ 750 ⁇ W/d 2 ; 50 ⁇ W/d 2 ⁇ L ⁇ 700 ⁇ W/d 2 ; 50 ⁇ W/d 2 ⁇ L ⁇ 650 ⁇ W/d 2 ; 50 ⁇ W/d 2 ⁇ L ⁇ 600 ⁇ W/d 2 ; 50 ⁇ W/d 2 ⁇ L ⁇ 550 ⁇ W/d 2 ; 50 ⁇ W/d 2 ⁇ L ⁇ 500 ⁇ W/d 2 ; 50 ⁇ W/d 2 ⁇ L ⁇ 450 ⁇ W/d 2 ; 50 ⁇ W/d 2 ⁇ L ⁇ 400 ⁇ W/d 2 ; 50 ⁇ W/d 2 ⁇ L ⁇ 350 ⁇ W/d 2 ;
  • L may satisfy the following formula: 40 ⁇ W/d 2 ⁇ L ⁇ 900 ⁇ W/d 2 ; more preferably, L may satisfy the following formula: 50 ⁇ W/d 2 ⁇ L ⁇ 800 ⁇ W /d 2 .
  • L may be equal to 30 ⁇ W/d 2 , 35 ⁇ W/d 2 , 40 ⁇ W/d 2 , 45 ⁇ W/d 2 , 50 ⁇ W/d 2 , 60 ⁇ W/d 2 , 70 ⁇ W/d 2 , 80 ⁇ W/d 2 , 90 ⁇ W/d 2 , 100 ⁇ W/d 2 , 150 ⁇ W/d 2 , 200 ⁇ W/d 2 , 250 ⁇ W/d 2 , 300 ⁇ W /d 2 , 350 ⁇ W/d 2 , 400 ⁇ W/d 2 , 450 ⁇ W/d 2 , 500 ⁇ W/d 2 , 550 ⁇ W/d 2 , 600 ⁇ W/d 2 , 650 ⁇ W/ d 2 , 700 ⁇ W/d 2 , 750 ⁇ W/d 2
  • the inventors of the present application have unexpectedly found that, satisfying the above conditions, the main catalyst and the cocatalyst can be well pre-contacted, and an ionic catalyst homogeneous solution with more excellent catalytic performance can be obtained.
  • the resulting homogeneous solution of the ionic catalyst after entering the reactor, is capable of producing the propylene-based copolymers of the present application, in particular propylene-based copolymers having the advantageous properties defined in the present application (especially the comonomer dispersion) thing.
  • the volume flow rate when the flow rates of the main catalyst mixed liquid and the co-catalyst mixed liquid are measured by a volume flow meter, the volume flow rate can be converted into a mass flow rate by using the density of the solvent.
  • the density of n-hexane is 0.66 g/cm 3 .
  • the volume flow rate can be converted into a mass flow rate through the density of n-hexane for use in the above formula.
  • the solvent used in the precontact is preferably at least one of C 4 -C 20 linear, branched or cyclic aliphatic hydrocarbons; At least one of pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, cyclopentane and cyclohexane; more preferably n-butane, iso- At least one of butane, n-pentane, isopentane, n-hexane, isohexane, cyclopentane and cyclohexane; more preferably n-pentane, isopentane, n-hexane, isohexane and cyclohexane At least one of ; more preferably n-hexane.
  • the procatalyst in the present application can be mixed with a solvent to obtain a procatalyst mixed solution.
  • the solvent is at least one of C 4 -C 20 linear, branched or cyclic aliphatic hydrocarbons; preferably n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane At least one of alkane, n-heptane, isoheptane, n-octane, isooctane, cyclopentane and cyclohexane; more preferably n-butane, isobutane, n-pentane, isopentane, At least one of n-hexane, isohexane, cyclopentane and cyclohexane; more preferably at least one of n-pentane, isopentane,
  • the concentration of the main catalyst mixed solution can be appropriately determined by those skilled in the art.
  • the concentration of the main catalyst mixed solution may be 0.001 ⁇ mol/mL to 1000 ⁇ mol/mL, preferably 0.01 ⁇ mol/mL to 100 ⁇ mol/mL.
  • the concentration of the main catalyst mixed solution may be 0.1 ⁇ mol/mL.
  • the cocatalyst in the present application can be mixed with a solvent to obtain a cocatalyst mixed solution.
  • the solvent is at least one of C 4 -C 20 linear, branched or cyclic aliphatic hydrocarbons; preferably n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane At least one of alkane, n-heptane, isoheptane, n-octane, isooctane, cyclopentane and cyclohexane; more preferably n-butane, isobutane, n-pentane, isopentane, At least one of n-hexane, isohexane, cyclopentane and cyclohexane; more preferably at least one of n-pentane, isopentane,
  • the concentration of the cocatalyst mixture can be appropriately determined by those skilled in the art.
  • the concentration of the cocatalyst mixture may be 0.001 ⁇ mol/mL to 1000 ⁇ mol/mL, preferably 0.01 ⁇ mol/mL to 100 ⁇ mol/mL.
  • the concentration of the co-catalyst mixture may be 0.15 ⁇ mol/mL.
  • the solvent of the main catalyst mixture is the same as the solvent of the co-catalyst mixture.
  • the solvent of the main catalyst mixed solution is the same as the solvent of the co-catalyst mixed solution, and the solvent is at least C 4 -C 20 linear, branched or cyclic aliphatic hydrocarbons One; preferably n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, cyclopentane and cyclohexane; more preferably at least one of n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, cyclopentane and cyclohexane; more
  • the preparation method of the propylene-based copolymer of the present invention comprises:
  • step (B) The ionic catalyst homogeneous solution obtained in step (A) is fed into the polymerization reactor through the pipeline connected to the polymerization reactor, and mixed with propylene monomer, one or more comonomers, Optional hydrogen contact, olefin polymerization, yields the propylene-based copolymer.
  • the preparation method of the present invention further comprises preparing the main catalyst mixed solution and the co-catalyst mixed solution before step (A).
  • preparing the procatalyst mixture includes mixing the procatalyst with a solvent, optionally with stirring.
  • preparing the cocatalyst mixture includes mixing the cocatalyst with a solvent, optionally with stirring. The stirring can use various stirring devices known in the art.
  • aromatic solvents such as toluene.
  • aromatic solvents have high boiling points and are not easily removed from polymers. If an aromatic solvent is introduced during a polymerization process, such as a solution polymerization process, it will result in the resulting polymer containing aromatic species. The presence of aromatics in the polymer has a detrimental effect on the application of the polymer, e.g. it cannot be used in the food and medical fields.
  • the propylene-based copolymer obtained by the preparation method of the present invention such as the propylene-based copolymer of the present invention, has an aromatic hydrocarbon compound weight content of less than 500 ppm, preferably less than 300 ppm, more preferably less than 200 ppm or less 100 ppm, further preferably less than 50 ppm, and most preferably no aromatic hydrocarbon compounds are present.
  • the "no use of aromatic hydrocarbon compounds” means that aromatic hydrocarbon compounds are not actively used in the method of the present invention.
  • the aromatic hydrocarbon compounds include those known in the art, such as benzene, toluene, ortho-xylene, meta-xylene, para-xylene, ethylbenzene, their halogenated derivatives, and their mixture.
  • the amount of the cocatalyst and the main catalyst can be the conventional amount in the art. Those skilled in the art can select the amount of the cocatalyst and the main catalyst.
  • the molar ratio of the central metal atom M in the cocatalyst to the main catalyst is 0.5:1-5:1, preferably 1:1-2:1.
  • an aluminum alkyl can be added to the olefin polymerization system.
  • the timing of adding the aluminum alkyl can be flexible, and it can be added to the pipeline or the polymerization reactor; preferably, it is added to the pipeline.
  • the aluminum alkyl is added after the beginning of the precontacting.
  • the aluminum alkyl is added downstream of the precontact point (ie closer to the polymerization reactor) in a line connected to the polymerization reactor where the precontacting takes place.
  • the aluminum alkyl used in the present invention can be a conventional aluminum alkyl in the art. According to some embodiments, the aluminum alkyl can have the structure of formula (III);
  • R is a C 1 -C 12 hydrocarbon group, preferably a C 1 -C 12 alkyl group, more preferably a C 1 -C 8 alkyl group.
  • the alkylaluminum may be at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, and triisooctylaluminum.
  • the alkylaluminum is added as an alkylaluminum solution.
  • the solvent of the alkylaluminum solution is a C 4 -C 20 linear, branched or cyclic aliphatic hydrocarbon; preferably, the solvent of the alkylaluminum solution is the same as the solvent used in the precontacting (ie, the solvent used to prepare the main catalyst mixture and the co-catalyst mixture) is the same.
  • the concentration of the alkylaluminum solution can vary within a wide range and can be appropriately selected by those skilled in the art; for example, it can be 1 to 20 mol/L.
  • both the boron-containing compound-based cocatalyst and the aluminum alkyl are used.
  • the olefin polymerization of the present invention may be in the form of bulk homogeneous polymerization, supercritical polymerization, solution polymerization, or near-critical dispersion polymerization. These modes of polymerization are known in the art.
  • the polymerization method of the present invention is solution polymerization.
  • the polymerization solvent may be a C 3 -C 10 alkane and/or a monocyclic aromatic hydrocarbon; preferably a C 3 -C 10 alkane.
  • the C 3 -C 10 alkanes are preferably propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, n-heptane, iso-heptane, n-octane, isooctane, At least one of cyclopentane and cyclohexane; the monocyclic aromatic hydrocarbon is preferably toluene and/or xylene.
  • the polymerization solvent is at least one or more of n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, cyclopentane and cyclohexane; more preferably n-butane At least one of pentane, isopentane, n-hexane, iso-hexane and cyclohexane; more preferably n-hexane.
  • the polymerization method of the present invention is solution polymerization, wherein the solvent employed in the solution polymerization is the same as that used to prepare the procatalyst mixture and/or the cocatalyst mixture.
  • the solvent used in the solution polymerization, the solvent used to prepare the main catalyst mixed solution and the solvent used to prepare the cocatalyst mixed solution are all the same; preferably, the solvent is At least one of C 4 -C 20 linear, branched or cyclic aliphatic hydrocarbons; preferably n-butane, isobutane, n-pentane, isopentane, n-hexane, iso-hexane, n-heptane At least one of alkane, isoheptane, n-octane, isooctane, cyclopentane and cyclohexane; more preferably n-butane, isobutane
  • the solvent used in the solution polymerization in the present invention is the same as the solvent used in the precontacting.
  • the solvent of the aluminum alkyl solution, the solvent used in the solution polymerization and the solvent used in the precontacting are all the same.
  • the polymerization in the present invention may be operated continuously or semi-continuously, and may also be operated in batches. These modes of operation are known in the art.
  • the polymerization of the present invention is preferably a continuous polymerization.
  • the olefin polymerization of the present invention can adopt the conventional process conditions in the art. Those skilled in the art can select suitable polymerization conditions according to the polymerization method employed, and these polymerization conditions are known in the art.
  • the polymerization temperature of the olefin polymerization in the present invention is between 60 and 150° C., and the polymerization pressure is between 0.1 and 10 MPa.
  • the polymerization can be terminated and post-treatment can be performed to obtain a polymer. Termination and work-up of polymerization reactions are known in the art.
  • compositions comprising propylene-based copolymers
  • the present invention provides a polymer composition comprising the propylene-based copolymer of the present invention; preferably the polymer composition comprises the propylene-based copolymer of the present invention and at least one additional polymer. Said additional polymer is different from the propylene-based copolymer of the present invention.
  • the polymer composition is a polypropylene composition and includes the propylene-based copolymer of the present invention and polypropylene.
  • the polypropylene includes polypropylene homopolymers, polypropylene copolymers other than the propylene-based copolymers of the present invention, or combinations thereof.
  • the present invention provides a polypropylene composition comprising:
  • the optional comonomers in the second polymer component are each independently selected from at least one of ethylene and C4 - C20 alpha-olefins.
  • the initial melting temperature of the polypropylene composition is above 80°C, preferably above 90°C; the melting enthalpy is below 50 J/g, preferably below 40 J/g.
  • Both the onset melting temperature and the melting enthalpy are determined by DSC.
  • the content of the propylene-based copolymer of the present invention and the content of the second polymer component in the polypropylene composition are calculated based on the total weight of the polypropylene composition.
  • the content of the propylene-based copolymer of the present invention is 50-99 wt %, and the content of the second polymer component is 1-50 wt %;
  • the content of the propylene-based copolymer of the present invention is 60-95 wt %, and the content of the second polymer component is 5-40 wt %.
  • the second polymer component preferably satisfies a certain degree of comonomer dispersion.
  • the dispersity D [PCP]/[C] of the structural units derived from comonomers contained in the second polymer component in the propylene segment is in the range of 50% to 75%; for example, 55% , 60%, 65%, 70%; wherein the degree of dispersion D [PCP]/[C] is as defined above.
  • the second polymer component can be prepared by the polymerization method of the present invention.
  • one or both of the propylene-based copolymer of the present invention and the second polymer component also have at least one of the following characteristics:
  • the range of mmm tacticity is between 75 and 99%, preferably between 80 and 97%;
  • the tacticity index m/r is 3-20.
  • the polypropylene composition of the present invention has a lower glass transition temperature.
  • the glass transition temperature of the polypropylene composition of the present invention is below -29°C, preferably below -30°C.
  • the glass transition temperature can be determined by DSC.
  • the polypropylene composition of the present invention contains the two polymer components, the polypropylene composition has only one melting peak on the DSC curve.
  • the polypropylene composition of the present invention can be characterized by the melting point (Tm). Melting points can be determined by differential scanning calorimetry (DSC).
  • the general procedure for DSC is: place 10 mg of sample in a crucible and measure on a differential scanning calorimeter (eg METTLER DSC1). Under a nitrogen atmosphere, the temperature was increased from -70°C to 200°C at a heating rate of 10°C/min, held for 1 min, lowered to -70°C at 10°C/min, held for 3 minutes, and then raised to 200°C at 10°C/min. Record the second heating scan data.
  • the maximum value of the highest temperature peak is considered to be the melting point of the polymer.
  • a “peak” in this context is defined as the change in the overall slope of the DSC curve (heat flow versus temperature) from positive to negative, forming a maximum on the baseline with no movement, where the DSC curve is drawn such that the end of the exothermic reaction Positive peaks will be displayed.
  • the melting point Tm (determined by DSC) of the polypropylene composition may be higher than 100°C and lower than 140°C, preferably lower than 130°C, more preferably lower than 120°C.
  • the polypropylene composition of the present invention can be characterized by the enthalpy of fusion ( ⁇ Hm).
  • the enthalpy of fusion can be determined by DSC.
  • the melting enthalpy of the polypropylene composition of the present invention is between 0.5 and 50 J/g, preferably between 5 and 40 J/g, more preferably between 10 and 30 J/g, most preferably between 15 and 25 J/g.
  • the crystallinity of the polypropylene composition of the present invention can be determined by dividing the ⁇ Hm of the sample by the ⁇ Hm of the 100% crystalline polymer.
  • the ⁇ Hm for a 100% crystalline polymer is assumed to be 189 J/g for isotactic polypropylene.
  • the crystallinity of the polypropylene composition of the present invention may be below 20%, preferably below 15%, more preferably between 5 and 12%.
  • the density of the polypropylene composition of the present invention is preferably 0.84-0.92 g/cc, more preferably 0.86-0.89 g/cc, measured by the ASTMD-1505 test method at room temperature.
  • the melt flow rate (MFR) of the polypropylene composition of the present invention at 190° C. under a load of 2.16kg can be lower than or equal to 100g/10min, preferably lower than or equal to 20g/10min; measured by ASTMD-1238 test method .
  • the polypropylene composition can be obtained by mixing the propylene-based copolymer of the present invention with the second polymer component in melt form or solution form.
  • These mixed forms are known in the art and can be selected and used in an appropriate manner by those skilled in the art.
  • the polypropylene composition of the present invention has a high comonomer content, and at the same time has a high initial melting temperature, which can avoid the problems of blocking and caking during storage and transportation.
  • the polypropylene composition of the present invention When the polypropylene composition of the present invention is blended with polypropylene, it can promote the crystallization of polypropylene. Therefore, in a polypropylene material comprising polypropylene and the polypropylene composition, the polypropylene composition can act as a polypropylene crystallization accelerator. Further, the mechanical properties of the polypropylene material can be improved. Therefore, the polypropylene composition can also be used as a modifier of the polypropylene material, specifically as a modifier of the mechanical properties of the polypropylene material.
  • the present invention also provides the use of the polypropylene composition in preparing a polypropylene material, the polypropylene material including polypropylene and the polypropylene composition.
  • the present invention also provides a polypropylene material, comprising polypropylene and the above-mentioned polypropylene composition.
  • the polypropylene composition and/or polypropylene material of the present invention may contain additives known in the art; for example fillers, antioxidants, surfactants, plasticizers, antiblocking agents, pigments, dyes, processing aids, UV stabilization agents, lubricants, waxes, nucleating agents, etc.
  • the additives may be present in typical effective amounts known in the art, eg, 0.001% to 10% by weight. Those skilled in the art can select and use these additives in a suitable manner.
  • Melt flow rate (190°C/2.16kg) is measured according to ASTM-D 1238 method.
  • Density is measured at room temperature according to ASTM-D792 method.
  • the mmm tacticity is measured by 13 C NMR; see the method in US Pat. No. 7,232,871.
  • Stereoregularity index m/r is measured by 13 C NMR; see the method described by HNCheng in Macromolecules, Vol. 17, pp. 1950-1955 (1984).
  • the melting point was determined by differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the general procedure for DSC is: place 10 mg of sample in a crucible and measure on a METTLER DSC1 differential scanning calorimeter. Under a nitrogen atmosphere, the temperature was increased from -70°C to 200°C at a heating rate of 10°C/min, held for 1 min, lowered to -70°C at 10°C/min, held for 3 minutes, and then raised to 200°C at 10°C/min. Record the second heating scan data. The maximum value of the highest temperature peak is considered to be the melting point of the polymer.
  • Polymerization activity The polymer obtained by polymerization is weighed after drying, and divided by the amount of catalyst added during polymerization to obtain the catalyst activity.
  • the enthalpy of fusion was determined by DSC as described above.
  • the polymerization reaction was carried out continuously in a 1.8L polymerization kettle.
  • the polymerization kettle is equipped with mechanical stirring, and the temperature of the polymerization kettle can be regulated by controlling the temperature of the jacket through an oil bath, and the temperature in the reactor is set at 90 °C.
  • the polymerization kettle is connected with a propylene line, an ethylene line, a n-hexane line and a catalyst injection line.
  • Solvent and monomer feeds into the reactor were measured by mass-flow controllers.
  • the hydrogen feed was incorporated into the ethylene line after passing through a mass-flow controller.
  • Variable speed diaphragm pumps control material flow and pressure.
  • the main catalyst is dimethylsilicon bis(5,6,7,8-tetrahydro-2,5,5,8,8-pentamethylbenzoindenyl)dimethylhafnium, and its synthesis method is shown in US Patent US60 /586465.
  • the main catalyst was mixed with n-hexane solvent, and the concentration of the obtained main catalyst mixed solution was 0.1 ⁇ mol/mL.
  • the boron-containing compound is a commercially available triphenylcarbonium tetrakis (pentafluorophenyl) boron compound, and the boron-containing compound is mixed with n-hexane solvent, and the concentration of the obtained boron-containing compound mixed solution is 0.15 ⁇ mol/mL.
  • the main catalyst mixed solution, the boron-containing compound mixed solution and the triisobutylaluminum solution were measured using a pump and a mass flow meter, and the main catalyst mixed solution and the boron-containing compound mixed solution were combined on the pipeline Afterwards, it entered the reactor via a pipeline with a length of 0.2 meters and an inner diameter (diameter) of 4.5 mm, and the triisobutylaluminum solution was then added to the pipeline at a distance of 0.1 meters from the reactor.
  • the reactor was operated at 30 bar with stirring.
  • the bottom of the polymerization kettle has a discharge line. Water was added to the discharge line along with tris(2,4-di-tert-butylphenyl)phosphite stabilizer to terminate the polymerization reaction.
  • the product material is then heated by a heat exchanger before entering a devolatilization unit. Polymer pellets were obtained using an extruder and an underwater pelletizer.
  • Example A1 The polymerization procedure of Example A1 is adopted, the difference is that the main catalyst mixed solution and the cocatalyst mixed solution are measured by a pump and a mass flow meter, and after being combined on the pipeline, enter the reactor through a pipeline with a length of 2 meters and an inner diameter (diameter) of 4.5 mm. .
  • Example A1 The polymerization procedure of Example A1 is adopted, except that the main catalyst is dimethylsilylbis(5,6,7,8-tetrahydro-2,5,5,8,8-pentamethylbenzoindenyl)bis Zirconium chloride, its synthetic method is referred to in US patent US60/586465.
  • the cocatalyst was MMAO-3A from Nouryon.
  • the main catalyst mixture and the co-catalyst mixture were measured using a pump and a mass flow meter, and after being combined on the pipeline, entered the reactor via a pipeline with a length of 0.5 m and an inner diameter (diameter) of 4.5 mm.
  • the propylene-based copolymers of Examples A1-A9 were incorporated into homopolypropylene (PP; PPH-M16 from Sinopec) for blending tests.
  • the weight ratio of propylene-based copolymer to PP was 13:87.
  • the dynamic mechanical curve (DMA curve) of the blend was measured using an RSA III DMA dynamic thermomechanical analyzer, and the glass transition temperature (Tg) of the blend was at the temperature of the tan delta peak.
  • Solid state testing was performed in dynamic mode with a torsion fixture in a liquid nitrogen environment. A ramp rate of 3°C/min, a frequency of 1 rad/sec, and an initial strain of 0.1% were used.
  • the average sample size is 45.0mm*12.6mm*3.2mm.
  • the compatibility of propylene-based copolymer with PP material can be reflected by the Tg peak on the DMA curve.
  • Each material obtained after blending has only one glass transition temperature peak on the DMA curve, and the crystallization temperature Tc of the PP material (obtained by DSC test) increases, indicating that the incorporation of the propylene-based copolymer of the present invention can promote PP crystals.
  • Figure A1 shows the dynamic mechanical curves of the polypropylene material before and after incorporating the propylene-based copolymer of Example A4 of the present invention, wherein the curve with a lower peak corresponding to the temperature is the polypropylene material after incorporating the sample of Example A4.
  • the material after blending the propylene-based copolymer of the present invention with PP has only one peak of glass transition temperature.
  • Figure A2 shows the dynamic mechanical curves of the polypropylene material before and after incorporating the propylene-based copolymer of Example A6 of the present invention, wherein the curve with a lower peak corresponding to the temperature is the polypropylene material after incorporating the sample of Example A6.
  • the material after blending the propylene-based copolymer of the present invention with PP has only one peak of glass transition temperature.
  • Figure A3 shows the crystallization temperature of polypropylene compositions incorporating the propylene-based copolymers of Examples A1-A4 and the propylene-based copolymers of Comparative Examples B2 and B3, where the weight ratio of propylene-based copolymer to polypropylene is 13:87.
  • the crystallization temperature Tc of the polypropylene composition obtained by DSC test
  • the crystallization temperatures of the polypropylene compositions were 117.9°C and 117.8°C.
  • the continuous polymerization was carried out in a 1.8L polymerization kettle.
  • the polymerization tank is equipped with mechanical stirring, and the temperature of the polymerization tank can be regulated by controlling the temperature of the jacket through an oil bath.
  • the polymerization kettle is connected with a propylene line, an ethylene line, a n-hexane line and a catalyst injection line.
  • Solvent and monomer feeds into the reactor were measured by mass-flow controllers. Material flow rate and pressure are controlled by a variable speed diaphragm pump.
  • the hydrogen feed was incorporated into the ethylene line after passing through a mass-flow controller.
  • the main catalyst is dimethylsilicon bis(5,6,7,8-tetrahydro-2,5,5,8,8-pentamethylbenzoindenyl)dimethylhafnium, and its synthesis method is shown in US Patent US60 /586465.
  • the main catalyst was mixed with n-hexane solvent, and the concentration of the obtained main catalyst mixed solution was 0.1 ⁇ mol/mL.
  • the boron-containing compound is a commercially available triphenylcarbonium tetrakis (pentafluorophenyl) boron compound.
  • the boron-containing compound is mixed with n-hexane solvent, and the concentration of the obtained boron-containing compound mixed solution is 0.15 ⁇ mol/mL.
  • the main catalyst mixed solution, the boron-containing compound mixed solution and the triisobutylaluminum solution were measured using a pump and a mass flow meter, and the main catalyst mixed solution and the boron-containing compound mixed solution were combined on the pipeline After that, it entered the polymerization kettle through a pipeline with a length of 0.2 m and an inner diameter (diameter) of 4.5 mm, and the triisobutylaluminum solution was subsequently added.
  • the reactor was operated with stirring.
  • the bottom of the polymerization kettle has a discharge line.
  • Example B1 The polymerization procedure of Example B1 is adopted, the difference is that the main catalyst mixed solution and the cocatalyst mixed solution are measured by a pump and a mass flow meter, and after being combined on the pipeline, enter the reactor through a pipeline with a length of 1 meter and an inner diameter (diameter) of 4.5 mm. .
  • Example B1 The polymerization procedure of Example B1 is adopted, the difference is that the main catalyst mixed solution and the cocatalyst mixed solution are measured by a pump and a mass flow meter, and after being combined on the pipeline, enter the reactor through a pipeline with a length of 2 meters and an inner diameter (diameter) of 4.5 mm. .
  • Example B1 The polymerization procedure of Example B1 was adopted, except that the main catalyst was dimethylsilylbis(5,6,7,8-tetrahydro-2,5,5,8,8-pentamethylbenzoindenyl)bis Zirconium chloride (refer to US patent US60/586465 for its synthesis method), and the cocatalyst is MMAO-3A product purchased from Nouryon Company.
  • the main catalyst mixture and the co-catalyst mixture were measured using a pump and a mass flow meter, and after being combined on the pipeline, entered the reactor via a pipeline with a length of 0.5 m and an inner diameter (diameter) of 4.5 mm.
  • the first polymer component i.e., the propylene-based copolymer of the present invention
  • the second polymer component in the polypropylene composition of the present invention were each prepared by continuous polymerization in a 1.8L polymerization tank.
  • the polymerization kettle is equipped with mechanical stirring, and the temperature of the polymerization kettle can be regulated by controlling the temperature of the jacket through an oil bath, and the temperature in the reactor is set at 90 °C.
  • the polymerization kettle is connected with a propylene line, an ethylene line, a n-hexane line and a catalyst injection line. Solvent and monomer feeds into the reactor were measured by mass-flow controllers. Variable speed diaphragm pumps control material flow and pressure.
  • the flow rate of propylene was 400 g/h
  • the flow rate of ethylene was 70 g/h
  • the flow rate of n-hexane was 600 g/h.
  • the flow rate of propylene was 390 g/h
  • the flow rate of ethylene was 12 g/h
  • the flow rate of n-hexane was 600 g/h.
  • the two polymer components were prepared from the same conditions as the procatalyst, cocatalyst, triisobutylaluminum.
  • the main catalyst is dimethylsilicon bis(5,6,7,8-tetrahydro-2,5,5,8,8-pentamethylbenzoindenyl)dimethylhafnium, and its synthesis method is shown in US Patent US60 /586465.
  • the main catalyst was mixed with n-hexane solvent, and the concentration of the obtained main catalyst mixed solution was 0.1 ⁇ mol/mL.
  • the boron-containing compound is a commercially available triphenylcarbonium tetrakis (pentafluorophenyl) boron compound.
  • the boron-containing compound is mixed with n-hexane solvent, and the concentration of the obtained boron-containing compound mixed solution is 0.15 ⁇ mol/mL.
  • the main catalyst mixture, the boron-containing compound mixture, and the triisobutylaluminum solution (a hexane solution with a concentration of 1 mmol/mL) were measured using a pump and a mass flow meter.
  • the flow rate of the main catalyst mixed solution was 60 mL/h, and the flow rate of the cocatalyst mixed solution was 50 mL/h.
  • the main catalyst mixed solution and the boron-containing compound mixed solution are combined on the pipeline, enter the reactor through a pipeline with a length of 0.2 meters and an inner diameter (diameter) of 4.5 mm, and the triisobutylaluminum solution (flow rate is 50mL/h) is then added to the pipeline. .
  • the reactor was operated at 30 bar with stirring.
  • the bottom of the polymerization kettle has a discharge line. Water was added to the discharge line along with tris(2,4-di-tert-butylphenyl)phosphite to terminate the polymerization reaction.
  • the first polymer component solution and the second polymer component solution obtained in the polymerization tank are mixed in a stirred tank, and then the blend material is heated by a heat exchanger and then enters a devolatilization device.
  • Polymer pellets were obtained using an extruder and an underwater pelletizer.
  • the first polymer component adopts the polymerization procedure of Example C1, the difference is that the main catalyst mixed solution and the co-catalyst mixed solution are measured by a pump and a mass flow meter, and after being combined on the pipeline, they are passed through a length of 2 meters and an inner diameter (diameter) of 4.5 meters. mm of the line into the reactor.
  • the second polymer component also used the same polymerization procedure as the first polymer component, but the main catalyst was dimethylsilylbisindenyl zirconium dichloride, and the cocatalyst was MMAO-3A purchased from Nouryon.
  • the main catalyst and the co-catalyst are not premixed on the pipeline, but directly enter the polymerization tank through their respective pipelines.
  • the first polymer component used the polymerization procedure of Example C1.
  • the second polymer component also used the same polymerization procedure as the first polymer component, but the main catalyst was dimethylsilylbisindenyl zirconium dichloride, and the cocatalyst was MMAO-3A purchased from Nouryon.
  • the main catalyst and the co-catalyst are not premixed on the pipeline, but directly enter the polymerization tank through their respective pipelines.
  • no comonomer was added, and propylene was homopolymerized.
  • Example B1 The polymerization procedure of Example B1 was adopted, except that the main catalyst was BCNX catalyst produced by Sinopec, and the co-catalyst was dicyclopentyldimethoxysilane.
  • the main catalyst mixture and the co-catalyst mixture were measured using a pump and a mass flow meter, and after being combined on the pipeline, entered the reactor via a pipeline with a length of 0.5 m and an inner diameter (diameter) of 4.5 mm.
  • the cocatalyst is MAO from Nouryon (toluene solution, active aluminum content is 1.5 mmol/mL).
  • the polymerization procedure of Example B1 was adopted, except that the main catalyst was dimethylsilylbis(5,6,7,8-tetrahydro-2,5,5,8,8-pentamethylbenzoindenyl)bis Zirconium chloride (see US Patent No. 60/586465 for its synthesis method), the cocatalyst is methylaluminoxane toluene solution.
  • the main catalyst mixture and the co-catalyst mixture were measured using a pump and a mass flow meter, and after being combined on the pipeline, entered the reactor via a pipeline with a length of 0.5 m and an inner diameter (diameter) of 4.5 mm.
  • Example B1 The polymerization procedure of Example B1 is adopted, the difference is that in Comparative Examples D7 and D8, the mixed solution of the main catalyst and the mixed solution of the co-catalyst were measured by a pump and a mass flow meter. mm of the line into the reactor.
  • Comparative Example D9 500 mL of the main catalyst mixed solution and 300 mL of the co-catalyst mixed solution were pre-mixed in a 1.2 L glass container with stirring for half an hour, and then injected into the reactor via a pump.
  • Example B1 The polymerization procedure of Example B1 was adopted, except that in Comparative Examples D10-D12, the main catalyst mixed solution and the cocatalyst mixed solution were measured by a pump and a mass flow meter, and after being combined on the pipeline, they passed through a pipeline with a length of 5 meters and an inner diameter of 4.5 mm. into the reactor.
  • Example B1 The polymerization procedure of Example B1 was adopted, except that the main catalyst was dimethylsilicon bis(2-methyl-4-phenylindenyl) zirconium dichloride (purchased from Panjin Yanfeng Technology Co., Ltd.), and the cocatalyst was Nouryon's MAO (toluene solution, active aluminum content of 1.5 mmol/mL). .
  • the main catalyst mixture and the co-catalyst mixture were measured using a pump and a mass flow meter, and after being combined on the pipeline, entered the reactor through a pipeline with a length of 0.5 m and an inner diameter of 4.5 mm.

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