Propylene polymer and synthesis method thereof
By introducing particularly large molecules and high standard catalyst components into the propylene polymer, the problem of difficult balance between strength and toughness of propylene polymer is solved, and a polymer with high flexural modulus and good toughness is achieved.
Patent Information
- Application Number
- CN202311349674.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-10-18
- Publication Date
- 2025-04-18
AI Technical Summary
Existing propylene polymers have difficulty achieving a good balance between strength and toughness, resulting in poor performance in some applications.
The regularity of the polymer and the regularity of the molecular chain are improved by introducing partially large molecules into the polymer and using high-quality catalyst components such as catalyst components containing magnesium, titanium and internal electron donors.
The high rigidity and toughness balance of propylene polymer is achieved, especially the increase in the flexural modulus, and the tensile yield stress and the impact strength of the cantilever beam notch are also significantly improved.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of olefin polymerization, and in particular to a propylene polymer and a synthesis method thereof. Background Art
[0002] Polypropylene is a polymer made from propylene as a monomer. It is non-toxic, odorless, low in density, and has excellent stiffness, hardness, and heat resistance. It has good electrical and insulating properties and is almost unaffected by humidity. Common acids, alkalis, and organic solvents have almost no effect on it. It is widely used in the automotive industry, household appliances, electronics, packaging machines, building materials, and furniture.
[0003] The polypropylene produced using the Ziegler-Natta catalyst is a mixture of polymers with different molecular weights and different molecular chain regularities. Generally speaking, the higher the polymer isotacticity, the more regular the molecular chain, the higher the polymer strength, but the polymer toughness will decrease. By reducing the isotacticity of the polymer, the toughness of the polymer will increase, but the strength of the polymer will decrease. In the present invention, the inventors have found a propylene polymer with excellent rigidity-toughness balance, especially a very high bending modulus. Summary of the invention
[0004] In view of the above problems, the present invention provides a propylene polymer, in which some molecules with particularly large molecular weight have high isotacticity and regular molecular chains, and the polymer has excellent rigidity-toughness balance, especially very high bending modulus.
[0005] The first aspect of the present invention provides a propylene polymer, wherein when the melt index of the propylene polymer is 2g / 10min-20g / 10min, the z-average molecular weight of the propylene polymer is ≥1 million; when the isotacticity of the propylene polymer is ≥96%, the mmmm% in the boiling heptane insoluble matter is ≥89%.
[0006] According to some embodiments of the present invention, when the melt index of the propylene polymer is between 2g / 10min and 5g / 10min, the z-average molecular weight of the propylene polymer is ≥1.5 million; when the isotacticity of the propylene polymer is ≥98%, the mmmm% in the boiling heptane insolubles is ≥91%.
[0007] According to some embodiments of the present invention, the propylene polymer has a bending modulus of elasticity ≧1.3 GPa, a tensile yield stress ≧32 MPa, and an Izod notched impact strength ≧40 J / m. Preferably, the propylene polymer has a bending modulus of elasticity ≧1.6 GPa, a tensile yield stress ≧35 MPa, and an Izod notched impact strength ≧40 J / m.
[0008] The melt index of the propylene polymer in the present invention is measured using a melt indexer at a temperature of 230° C. and a pressure of 2.16 kg according to ASTM D1238-99 “Standard Test Method for Melt Flow Rate of Thermoplastics Using an Extrusion Plastometer”;
[0009] The z-average molecular weight of the propylene polymer is measured by GPC test, specifically by using a Waters Alliance GPC2000 gel permeation chromatograph from Waters Company, using 1,2,4-trichlorobenzene as solvent and styrene as standard sample;
[0010] The isotacticity of the propylene polymer is measured by boiling heptane extraction method.
[0011] The second aspect of the present invention provides a catalyst component for preparing the above-mentioned propylene polymer, wherein the catalyst component is a reaction product comprising the following components or the following components:
[0012] (1) magnesium compounds,
[0013] (2) Titanium-containing compounds,
[0014] (3) Internal electron donor compounds;
[0015] Wherein, the internal electron donor is selected from glycol ester compounds; the content of the meso form in the catalyst component is ≧95%, preferably ≧98%.
[0016] According to some embodiments of the present invention, the diol ester compound is selected from the diol ester compound represented by formula (I);
[0017]
[0018] In formula (I), R1 and R2 are the same or different and are independently selected from substituted or unsubstituted C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C6-C 20 Alkyl, C6-C 20 Aralkyl, C2-C 20 Alkenyl and C4-C 20 A is selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C1-C 20 Cycloalkyl or C1-C 20 A divalent aromatic group.
[0019] According to some embodiments of the present invention, the diol ester compound represented by formula (I) is selected from 2,4-pentanediol dibenzoate, 2,4-pentanediol di-n-propyl benzoate, 2,4-pentanediol diisopropyl benzoate, 2,4-pentanediol di-n-butyl benzoate, 2,4-pentanediol diisobutyl benzoate, 3,5-heptanediol dibenzoate, 3,5-heptanediol di-n-propyl benzoate, 3,5-heptanediol diisopropyl benzoate, 3,5-heptanediol di-n-butyl benzoate, 3,5-heptanediol diisobutyl benzoate, 4-ethyl-3,5-heptanediol dibenzoate, 3,5-heptanediol di-p-methyl benzoate, 3,5-heptanediol di-o-methyl benzoate, 3,5-heptanediol di-p-chlorobenzoate , 3,5-heptanediol di-o-chlorobenzoate, 3,5-heptanediol di-p-methoxybenzoate, 3,5-heptanediol di-o-methoxybenzoate, 3,5-heptanediol di-m-methoxybenzoate, 2-methyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-heptanediol dibenzoate, 6-methyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 5-ethyl-3,5-heptanediol dibenzoate, 4-propyl-3,5-heptanediol dibenzoate, 4-butyl-3,5-heptanediol dibenzoate, 2,4-dimethyl-3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate diol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 4,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 2-methyl-4-ethyl-3,5-heptanediol dibenzoate, 4-methyl-4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-4-propyl-3,5-heptanediol dibenzoate, 4-methyl-4-propyl-3,5-heptanediol dibenzoate, 6-methyl-2,4-heptanediol di(p-methylbenzoate), 6-methyl-2,4-heptanediol di(m-methylbenzoate), 2,2,6,6-tetramethyl-3,5-heptanediol 4-Methyl-3,5-octanediol dibenzoate, 4-ethyl-3,5-octanediol dibenzoate, 4-propyl-3,5-octanediol dibenzoate, 4-butyl-3,5-octanediol dibenzoate, 4,4-dimethyl-3,5-octanediol dibenzoate, 4-methyl-4-ethyl-3,5-octanediol dibenzoate, 2-methyl-4-ethyl-3,5-octanediol dibenzoate, 2-methyl-6-ethyl-3,5-octanediol dibenzoate, 5-methyl-4,6-nonanediol dibenzoate, 5-ethyl-4,6-nonanediol dibenzoate, 5-propyl-4,6-nonanediol dibenzoate, 5-butyl-4,6-nonanediol dibenzoate, 5,5-dimethyl-4,6-nonanediol dibenzoate, 5-methyl-4-ethyl-4,6-nonanediol dibenzoate, 5-phenyl-4,6-nonanediol dibenzoate, 4,6-nonanediol dibenzoate and 4-butyl-3,5-heptanediol dibenzoate, 1,2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1,2-phenylene dibenzoate, 3,5-diisopropyl-1,2-phenylene dibenzoate, 3,6-dimethyl-1,2-phenylene dibenzoate, 4-tert-butyl-1,2-phenylene dibenzoate, 1,2-naphthalene dibenzoate, 2,3-naphthalene dibenzoate At least one of the following esters: 1,8-naphthyl dibenzoate, 1,8-naphthyl di-4-methylbenzoate, 1,8-naphthyl di-3-methylbenzoate, 1,8-naphthyl di-2-methylbenzoate, 1,8-naphthyl di-4-ethylbenzoate, 1,8-naphthyl di-4-n-propylbenzoate, 1,8-naphthyl di-4-isopropylbenzoate, 1,8-naphthyl di-4-n-butylbenzoate, 1,8-naphthyl di-4-isobutylbenzoate, 1,8-naphthyl di-4-tert-butylbenzoate, and 1,8-naphthyl di-4-phenylbenzoate.
[0020] According to some embodiments of the present invention, the magnesium-containing compound is selected from magnesium dihalide, alkoxy magnesium, alkyl magnesium, hydrate of magnesium dihalide, alcoholate of magnesium dihalide or a derivative in which one halogen atom in the magnesium dihalide molecular formula is replaced by an alkoxy group or a haloalkoxy group; preferably, the magnesium-containing compound is selected from magnesium dihalide or alcoholate of magnesium dihalide; further preferably, the magnesium-containing compound is selected from at least one of magnesium dichloride, magnesium dibromide, magnesium diiodide, alcoholate of magnesium dichloride, alcoholate of magnesium dibromide and alcoholate of magnesium diiodide.
[0021] According to some embodiments of the present invention, the general formula of the titanium-containing compound is TiX m (OR 1 ) 4-m , where R 1 Selected from C1-C 20 A hydrocarbon group, X is a halogen, 1≤m≤4; preferably, the titanium-containing compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, triethoxytitanium monochloride, diethoxytitanium dichloride and triethoxytitanium monochloride.
[0022] According to some embodiments of the present invention, the present invention has no particular limitation on the content of magnesium, titanium and internal electron donor in the catalyst component, which can be any value of the content in conventional catalyst components in the art; preferably, the molar ratio of the amount of magnesium source calculated as magnesium element, the amount of titanium source calculated as titanium element and the amount of internal electron donor compound is 1:(15-150):(0.1-0.9), preferably 1:(25-120):(0.15-0.6).
[0023] According to some embodiments of the present invention, the catalyst component of the present invention can be prepared by the following method, but the preparation method of the catalyst component involved in the present invention is not limited thereto.
[0024] First, a magnesium-containing compound is dissolved in a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and an inert diluent to form a uniform solution, and then mixed with a precipitation agent in the presence of a precipitation aid, and the temperature is increased to precipitate a solid; the solid is then treated with an electron donor compound so that it (the electron donor compound) is attached to the solid, and then the solid is treated with titanium tetrahalide or titanium tetrahalide and an inert diluent.
[0025] According to some embodiments of the present invention, in the present invention, the precipitation agent is a metal halide. In the above method, the precipitation agent can be selected from metal halides, such as titanium halide, iron halide, zinc halide, etc.; among them, titanium halide, such as titanium tetrachloride or titanium tetrabromide, etc. is preferred; titanium tetrachloride is more preferred.
[0026] According to some embodiments of the present invention, in the present invention, the precipitation aid is selected from oxygen-containing compounds, preferably selected from acid anhydrides and diester compounds; further preferably selected from acid anhydrides and malonate diester compounds, such as phthalic anhydride.
[0027] According to some embodiments of the present invention, in the present invention, the organic epoxy compound is selected from aliphatic olefins, dienes or halogenated aliphatic olefins having 2 to 8 carbon atoms substituted by heteroatoms; specific compounds include epichlorohydrin, epibromohydrin, etc.
[0028] The third aspect of the present invention provides a method for synthesizing the above-mentioned propylene polymer, comprising polymerizing propylene under olefin polymerization conditions in the presence of a catalyst and hydrogen, wherein the catalyst comprises the above-mentioned catalyst component, an alkyl aluminum compound and an optional external electron donor compound.
[0029] According to some embodiments of the present invention, the general formula of the alkyl aluminum compound is AlR n X 3-n , wherein R is hydrogen or a C1-C20 hydrocarbon group, X is a halogen, and n is a number of 1<n≤3; preferably, the alkyl aluminum compound is selected from triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydrogenate, diisobutylaluminum monohydrogenate, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride and ethylaluminum dichloride, preferably triethylaluminum and triisobutylaluminum.
[0030] According to some embodiments of the present invention, the external electron donor compound is selected from the group consisting of: k Si(OR4) 4-kThe organosilicon compound, wherein 0≤k≤3, R3 is selected from halogen, hydrogen atom, amino group, substituted or unsubstituted C1-C 20 Straight chain alkyl, substituted or unsubstituted C1-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, R4 is selected from amino, substituted or unsubstituted C1-C 20 Straight chain alkyl, substituted or unsubstituted C1-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl; Preferably, the organosilicon compound is selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane and methyl-tert-butyldimethoxysilane.
[0031] A fourth aspect of the present invention provides use of the above catalyst component in propylene polymerization, wherein during the propylene polymerization, the polymerization pressure is ≧2 MPa, preferably ≧3 MPa.
[0032] Beneficial effects:
[0033] The object of the present invention is to provide a propylene polymer, wherein some molecules of particularly large molecular weight are present in the polymer, and the molecular chains of these large molecules are relatively regular, and the polymer has excellent rigidity-toughness balance, especially high modulus. DETAILED DESCRIPTION
[0034] The present invention will be further described below in conjunction with the embodiments, but the present invention is not limited by these embodiments.
[0035] If no specific conditions are specified in the examples of the present invention, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.
[0036] The endpoints and any values of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and the individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.
[0037] In the embodiments of the present invention, the heating process is not specifically limited, and any known method may be used for heating, such as slow, step-by-step, fast or programmed heating. The specific heating method is adjusted according to the specific formulation, contact temperature, etc.
[0038] According to the preparation method of the present invention, when other conditions are the same, different heating processes will affect the particle morphology, particle size distribution, activity of the catalyst and properties of the polymer of the final catalyst; specifically, a slower heating process can obtain a better particle morphology, conversely, too fast a heating rate will lead to a deterioration of the particle shape and a decrease in sphericity, etc.
[0039] In the embodiments of the present invention, the melt index MI of the propylene polymer is measured using a melt indexer at a temperature of 230° C. and a pressure of 2.16 kg according to ASTM D1238-99 “Standard Test Method for Melt Flow Rate of Thermoplastics Using an Extrusion Plastometer”.
[0040] In the embodiment of the present invention, the z-average molecular weight (Mz) of the propylene polymer is measured by GPC test, specifically by using Waters Alliance GPC2000 gel permeation chromatograph produced by Waters Company, with 1,2,4-trichlorobenzene as solvent and styrene as standard sample.
[0041] In the embodiments of the present invention, the isotacticity of the propylene polymer is determined by a boiling heptane extraction method.
[0042] In the embodiments of the present invention, the test standards for the tensile yield stress, flexural elastic modulus and notched cantilever impact strength of the propylene polymer are all GB / T12670-2008.
[0043] In the embodiment of the present invention, the meso content of the internal electron donor compound is measured using a Waters 600E high performance liquid chromatograph.
[0044] Example 1
[0045] This embodiment provides a catalyst component for preparing a propylene polymer.
[0046] The preparation method is as follows:
[0047] In a reactor fully replaced with high-purity nitrogen, add 4.8g of magnesium chloride, 98mL of toluene, 4mL of epichlorohydrin, and 12.5mL of tributyl phosphate in sequence, raise the temperature to 50°C with stirring, and maintain for 2.5h, then add 1.4g of phthalic anhydride, and continue to maintain for 1h; cool the solution to below -25°C, and add TiCl4 dropwise within 1h. 56mL, slowly raise the temperature to 80°C to precipitate a solid; add 6mmol of internal electron donor compound A (3,5-heptanediol di-n-propyl benzoate) to the solid, maintain the temperature for 1h, filter, and wash twice with 70mL of toluene to obtain a solid precipitate; then add TiCl4 / toluene solution to the precipitate (in the TiCl4 / toluene solution, TiCl4 is 40ml and toluene is 60ml), raise the temperature to 110°C, maintain for 1h, filter, and repeat the same operation four times; then wash the filtered precipitate three times with 70mL of toluene at a temperature of 100°C, each time for 10min, and finally wash twice with 60mL of hexane to obtain a catalyst component for preparing a propylene polymer, wherein the meso content in the catalyst component for preparing a propylene polymer is 100%.
[0048] This embodiment further provides a method for synthesizing a propylene polymer.
[0049] Here are the steps:
[0050] A stainless steel reactor with a volume of 5 L was fully replaced with gaseous propylene, and then 2.5 mmol of AlEt3 and 0.1 mmol of the required external electron donor compound (methylcyclohexyldimethoxysilane) were added. Then, 10 mg of the catalyst component prepared in Example 1 and 1.2 L of hydrogen were added, and 2.3 L of liquid propylene (polymerization pressure 3.1 MPa) was introduced. The temperature was raised to 70°C and maintained at this temperature for 1 hour; the temperature was lowered and the pressure was released to obtain a propylene polymer, i.e., PP powder.
[0051] Example 2
[0052] This embodiment provides a catalyst component for preparing a propylene polymer.
[0053] The preparation method is the same as Example 1.
[0054] This embodiment further provides a method for synthesizing a propylene polymer.
[0055] The steps were the same as those in Example 1, except that the amount of hydrogen added was adjusted from 1.2 L to 1.8 L (polymerization pressure 3.2 MPa).
[0056] Example 3
[0057] This embodiment provides a catalyst component for preparing a propylene polymer.
[0058] The preparation method is the same as that of Example 1, except that the meso content of the catalyst component for preparing the propylene polymer is 98.4%.
[0059] This embodiment further provides a method for synthesizing a propylene polymer.
[0060] The steps are the same as in Example 1.
[0061] Comparative Example 1
[0062] This comparative example provides a propylene polymer, which is a commercially available polypropylene (brand number T30s).
[0063] Comparative Example 2
[0064] This comparative example provides a catalyst component for preparing a propylene polymer.
[0065] The preparation method is the same as that of Example 1, except that the meso content of the catalyst component for preparing the propylene polymer is 90%.
[0066] This comparative example further provides a method for synthesizing a propylene polymer.
[0067] The steps are the same as in Example 1.
[0068] Example 4
[0069] This embodiment provides a catalyst component for preparing a propylene polymer.
[0070] The preparation method is the same as that of Example 1, except that the internal electron donor compound A (3,5-heptanediol di-n-propyl benzoate) is replaced by the internal electron donor compound B (3,5-heptanediol di-n-butyl benzoate), and the meso content of the prepared catalyst component for preparing propylene polymer is 100%.
[0071] This embodiment further provides a method for synthesizing a propylene polymer.
[0072] The steps are the same as those in Example 1, except that the amount of hydrogen added is adjusted from 1.2 L to 3.0 L (polymerization pressure 3.4 MPa).
[0073] Comparative Example 3
[0074] This comparative example provides a propylene polymer, which is a commercially available polypropylene (brand number V30G).
[0075] Example 5
[0076] This embodiment provides a catalyst component for preparing a propylene polymer.
[0077] The preparation method is the same as Example 4.
[0078] This embodiment further provides a method for synthesizing a propylene polymer.
[0079] The steps are the same as those of Example 1, except that 0.025 mmol of the external electron donor compound (methylcyclohexyldimethoxysilane) is used to replace 0.1 mmol of the external electron donor compound (methylcyclohexyldimethoxysilane).
[0080] Example 6
[0081] This embodiment provides a catalyst component for preparing a propylene polymer.
[0082] The preparation method is the same as that of Example 1, except that the internal electron donor compound A (3,5-heptanediol di-n-propyl benzoate) is replaced by the internal electron donor compound E (2,4-pentanediol dibenzoate), and the meso content of the prepared catalyst component for preparing propylene polymer is 100%.
[0083] This embodiment further provides a method for synthesizing a propylene polymer.
[0084] The steps are the same as in Example 1.
[0085] Example 7
[0086] This embodiment provides a catalyst component for preparing a propylene polymer.
[0087] The preparation method is the same as that of Example 1, except that the internal electron donor compound A (3,5-heptanediol di-n-propyl benzoate) is replaced by the internal electron donor compound F (2,4-pentanediol di-n-propyl benzoate), and the meso content in the prepared catalyst component for preparing propylene polymer is 100%.
[0088] This embodiment further provides a method for synthesizing a propylene polymer.
[0089] The steps are the same as in Example 1.
[0090] Example 8
[0091] This embodiment provides a catalyst component for preparing a propylene polymer.
[0092] The preparation method is the same as that of Example 1, except that the internal electron donor compound A (3,5-heptanediol di-n-propyl benzoate) is replaced by the internal electron donor compound B (3,5-heptanediol di-n-butyl benzoate), and the meso content of the prepared catalyst component for preparing propylene polymer is 95.8%.
[0093] This embodiment further provides a method for synthesizing a propylene polymer.
[0094] The steps are the same as in Example 1.
[0095] Comparative Example 4
[0096] This comparative example provides a catalyst component for preparing a propylene polymer.
[0097] The preparation method is the same as that of Example 1, except that the internal electron donor compound A (3,5-heptanediol di-n-propyl benzoate) is replaced by the internal electron donor compound H (di-n-butyl phthalate), and the prepared catalyst component for preparing propylene polymer does not contain meso.
[0098] This comparative example further provides a method for synthesizing a propylene polymer.
[0099] The steps are the same as in Example 1.
[0100] Comparative Example 5
[0101] This comparative example provides a catalyst component for preparing a propylene polymer.
[0102] The preparation method is the same as Example 1.
[0103] This comparative example further provides a method for synthesizing a propylene polymer.
[0104] The steps are the same as those in Example 1, except that the polymerization pressure is 0.5 MPa.
[0105] In order to further illustrate the progress of the present invention, the propylene polymers prepared in the above Examples 1-8 and Comparative Examples 1-5 are now subjected to performance tests, and the test results are statistically shown in the following Table 1;
[0106] Table 1
[0107]
[0108]
[0109] It can be seen from the test results in Table 1 that the propylene polymer synthesized by the catalyst component for preparing propylene polymer prepared by the present invention has high rigidity, high toughness and strength, and a very good rigid-toughness balance when the melt index of the propylene polymer is 2g / 10min-20g / 10min, the z-average molecular weight of the propylene polymer is ≧1,000,000; and when the isotacticity of the propylene polymer is ≧96%, and the mmmm% in the boiling heptane insolubles is ≧89%, which is conducive to the development of high value-added polypropylene products.
[0110] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.
Claims
1. A propylene polymer, characterized in that When the melt index of the propylene polymer is between 2g / 10min and 20g / 10min, the z-average molecular weight of the propylene polymer is greater than or equal to 1 million; when the isotacticity of the propylene polymer is greater than or equal to 96%, the mmmm% in the boiling heptane insoluble matter is greater than or equal to 89%.
2. The propylene polymer according to claim 1, characterized in that When the melt index of the propylene polymer is between 2g / 10min and 5g / 10min, the z-average molecular weight of the propylene polymer is ≥1.5 million; when the isotacticity of the propylene polymer is ≥98%, the mmmm% in the boiling heptane insoluble matter is ≥91%.
3. The propylene polymer according to claim 1 or 2, characterized in that The propylene polymer has a bending elastic modulus of ≧1.3 GPa, preferably ≧1.6 GPa, a tensile yield stress of ≧32 MPa, preferably ≧35 MPa, and an Izod notched impact strength of ≧40 J / m.
4. A catalyst component for preparing the propylene polymer according to any one of claims 1 to 3, characterized in that The catalyst component is a component comprising the following or a reaction product of the following: (1) magnesium compounds, (2) Titanium-containing compounds, (3) Internal electron donor compounds; Wherein, the internal electron donor is selected from glycol ester compounds; the content of the meso form in the catalyst component is ≧95%, preferably ≧98%.
5. The catalyst component according to claim 4, characterized in that The diol ester compound is selected from the diol ester compound represented by formula (I); In formula (I), R1 and R2 are the same or different and are independently selected from substituted or unsubstituted C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C6-C 20 Alkyl, C6-C 20 Aralkyl, C2-C 20 Alkenyl and C4-C 20 A is selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C1-C 20 Cycloalkyl or C1-C 20 A divalent aromatic group.
6. The catalyst component according to claim 4 or 5, characterized in that The diol ester compound represented by formula (I) is selected from 2,4-pentanediol dibenzoate, 2,4-pentanediol di-n-propyl benzoate, 2,4-pentanediol diisopropyl benzoate, 2,4-pentanediol di-n-butyl benzoate, 2,4-pentanediol diisobutyl benzoate, 3,5-heptanediol dibenzoate, 3,5-heptanediol di-n-propyl benzoate, 3,5-heptanediol diisopropyl benzoate, 3,5-heptanediol di-n-butyl benzoate, 3,5-heptanediol diisobutyl benzoate, 4-ethyl-3,5-heptanediol dibenzoate, 3,5-heptanediol di-p-methyl benzoate, 3,5-heptanediol di-o-methyl benzoate, 3,5-heptanediol di-p-chlorobenzoate, 3,5-heptanediol di-o-chlorobenzoate , 3,5-heptanediol di-p-methoxybenzoate, 3,5-heptanediol di-o-methoxybenzoate, 3,5-heptanediol di-m-methoxybenzoate, 2-methyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-heptanediol dibenzoate, 6-methyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 5-ethyl-3,5-heptanediol dibenzoate, 4-propyl-3,5-heptanediol dibenzoate, 4-butyl-3,5-heptanediol dibenzoate, 2,4-dimethyl-3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3 ,5-heptanediol dibenzoate, 4,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 2-methyl-4-ethyl-3,5-heptanediol dibenzoate, 4-methyl-4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-4-propyl-3,5-heptanediol dibenzoate, 4-methyl-4-propyl-3,5-heptanediol dibenzoate, 6-methyl-2,4-heptanediol di(p-methylbenzoate), 6-methyl-2,4-heptanediol di(m-methylbenzoate), 2,2,6,6-tetramethyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-octanediol dibenzoate, 4-ethyl-3,5-octanediol dibenzoate, 4-propyl-3,5-octanediol dibenzoate, 4-butyl-3,5-octanediol dibenzoate, 4,4-dimethyl-3,5-octanediol dibenzoate, 4-methyl-4-ethyl-3,5-octanediol dibenzoate, 2-methyl-4-ethyl-3,5-octanediol dibenzoate, 2-methyl-6-ethyl-3,5-octanediol dibenzoate, 5-methyl-4,6-nonanediol dibenzoate, 5-ethyl-4,6-nonanediol dibenzoate, 5-propyl-4,6-nonanediol dibenzoate, 5-butyl-4,6-nonanediol dibenzoate, 5,5-dimethyl-4,6-nonanediol dibenzoate, 5-methyl-4-ethyl-4,6-nonanediol dibenzoate, 5-phenyl-4,6-nonanediol dibenzoate, 4,6-nonanediol dibenzoate and 4-butyl-3,5-heptanediol dibenzoate, 1,2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1,2-phenylene dibenzoate, 3,5-diisopropyl-1,2-phenylene dibenzoate, 3,6-dimethyl-1,2-phenylene dibenzoate, 4-tert-butyl-1,2-phenylene dibenzoate, 1,2-naphthalene dibenzoate, 2,3-naphthalene dibenzoate-1,8 -naphthyl ester, di-4-methylbenzoic acid-1,8-naphthyl ester, di-3-methylbenzoic acid-1,8-naphthyl ester, di-2-methylbenzoic acid-1,8-naphthyl ester, di-4-ethylbenzoic acid-1,8-naphthyl ester, di-4-n-propylbenzoic acid-1,8-naphthyl ester, di-4-isopropylbenzoic acid-1,8-naphthyl ester, di-4-n-butylbenzoic acid-1,8-naphthyl ester, di-4-isobutylbenzoic acid-1,8-naphthyl ester, di-4-tert-butylbenzoic acid-1,8-naphthyl ester, di-4-phenylbenzoic acid-1,8-naphthyl ester.
7. The catalyst component according to any one of claims 4 to 6, characterized in that The magnesium-containing compound is selected from magnesium dihalide, alkoxymagnesium, alkylmagnesium, hydrate of magnesium dihalide, alcoholate of magnesium dihalide or a derivative in which one halogen atom in the magnesium dihalide molecular formula is replaced by an alkoxy group or a haloalkoxy group; preferably, the magnesium-containing compound is selected from magnesium dihalide or alcoholate of magnesium dihalide; further preferably, the magnesium-containing compound is selected from at least one of magnesium dichloride, magnesium dibromide, magnesium diiodide, alcoholate of magnesium dichloride, alcoholate of magnesium dibromide and alcoholate of magnesium diiodide.
8. The catalyst component according to any one of claims 4 to 7, characterized in that The general formula of the titanium-containing compound is TiX m (OR 1 ) 4-m , where R 1 Selected from C1-C 20 A hydrocarbon group, X is a halogen, 1≤m≤4; preferably, the titanium-containing compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium triethoxide monochloride, titanium diethoxide dichloride, titanium triethoxide monochloride; And / or, the molar ratio of the magnesium source calculated as magnesium element, the titanium source calculated as titanium element and the internal electron donor compound is 1:(15-150):(0.1-0.9), preferably 1:(25-120):(0.15-0.6).
9. A method for synthesizing a propylene polymer according to any one of claims 1 to 3, comprising polymerizing propylene in the presence of a catalyst and hydrogen, characterized in that: The catalyst comprises the catalyst component according to any one of claims 4 to 8, an alkyl aluminum compound and optionally an external electron donor compound.
10. The synthesis method according to claim 9, characterized in that The general formula of the alkyl aluminum compound is AlR n X 3-n , wherein R is hydrogen or a C1-C20 hydrocarbon group, X is a halogen, and n is a number of 1<n≤3; preferably, the alkyl aluminum compound is selected from at least one of triethyl aluminum, tripropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-n-octylaluminum, triisobutyl aluminum, diethyl aluminum monohydrogenate, diisobutyl aluminum monohydrogenate, diethyl aluminum monochloride, diisobutyl aluminum monochloride, sesquiethyl aluminum chloride, and ethyl aluminum dichloride; And / or, the external electron donor compound is selected from the general formula (R3) k Si(OR4) 4-k The organosilicon compound, wherein 0≤k≤3, R3 is selected from halogen, hydrogen atom, amino group, substituted or unsubstituted C1-C 20 Straight chain alkyl, substituted or unsubstituted C1-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, R4 is selected from amino, substituted or unsubstituted C1-C 20 Straight chain alkyl, substituted or unsubstituted C1-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl; Preferably, the organosilicon compound is selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane and methyl-tert-butyldimethoxysilane.
11. Use of the catalyst component according to any one of claims 4 to 8 in propylene polymerization, wherein during the propylene polymerization, the polymerization pressure is ≧2 MPa, preferably ≧3 MPa.