Ethylene / propylene random polymer and synthesis method thereof

Abstract

The invention discloses an ethylene / propylene random polymer, relates to the technical field of olefin polymerization, and particularly relates to an ethylene / propylene random polymer and a synthesis method thereof. The molar weight of boiling heptane insoluble fraction ethylene in the ethylene / propylene random polymer is greater than or equal to 0.5%, and the molar content of normal-temperature octane soluble fraction ethylene is less than or equal to 11%; the tensile elastic modulus of the ethylene / propylene random polymer is greater than or equal to 700Mpa, and the simply supported beam impact strength is greater than or equal to 51KJ / m < 2 >; according to the ethylene / propylene random polymer, the content of ethylene in high molecular weight is higher than that of an existing polymer, meanwhile, the content of ethylene in low molecular weight is lower than that of the existing polymer, and the obtained polymer is very excellent in rigidity and toughness and good in rigidity-toughness balance performance; the invention also provides a synthesis method of the ethylene / propylene random copolymer, and the synthesis of the ethylene / propylene random copolymer can be carried out in one reactor, so that the operation is simpler, and energy conservation and emission reduction are more facilitated.

Description

Technical Field

[0001] The invention relates to the technical field of olefin polymerization, and in particular to an ethylene / propylene random polymer and a synthesis method thereof. Background Art

[0002] Polypropylene is a polymer made of propylene as a monomer. It is non-toxic, odorless, low in density, excellent in stiffness, hardness, and heat resistance, and has good electrical and insulating properties. It is almost unaffected by humidity, and 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. However, homopolymer polypropylene generally has the disadvantages of being brittle at low temperatures and having poor impact resistance. In order to improve its impact resistance, develop special materials that meet market demand, and expand the application field of polypropylene, it is generally adopted to add ethylene monomers during the propylene polymerization process to achieve the purpose of modification through copolymerization.

[0003] In ethylene / propylene random copolymers, the ideal molecular chain structure is that ethylene is distributed in the high molecular weight segment, and there is no ethylene or the ethylene content is low in the low molecular weight segment. In actual production, the ethylene content in the high molecular weight segment is usually very low, while the ethylene content in the low molecular weight part is very high. This greatly reduces the tensile strength and modulus of the polymer while improving the impact resistance of the polymer. Summary of the invention

[0004] The present invention aims at the above-mentioned problems and provides an ethylene / propylene random polymer and a synthesis method thereof. The prepared ethylene / propylene random polymer has a higher content of ethylene in high molecular weight than the existing polymer and a lower content of ethylene in low molecular weight than the existing polymer. The present invention also provides a synthesis method of an ethylene / propylene random copolymer. The synthesis of the ethylene / propylene random copolymer can be carried out in one reactor, which is simpler to operate and more conducive to energy conservation and emission reduction.

[0005] To solve the above technical problems, the first aspect of the present invention provides an ethylene / propylene random polymer, wherein the molar amount of ethylene in the boiling heptane insoluble fraction is ≥ 0.5%, and the molar content of ethylene in the room temperature octane soluble fraction is ≤ 11%.

[0006] According to some embodiments of the present invention, the molar amount of ethylene in the boiling heptane insoluble fraction of the ethylene / propylene random polymer is ≧1%, and the molar content of ethylene in the room temperature octane soluble fraction is ≦10%.

[0007] According to some embodiments of the present invention, the tensile elastic modulus of the ethylene / propylene random polymer is ≥ 700 MPa, and the simply supported beam impact strength is ≥ 51 KJ / m 2 .

[0008] According to some embodiments of the present invention, the tensile elastic modulus of the ethylene / propylene random polymer is ≥ 700 MPa, and the simply supported beam impact strength is ≥ 55 KJ / m 2 .

[0009] In the present invention, the room temperature octane soluble fraction of the ethylene / propylene random polymer is obtained according to the following method: 150 mL of n-octane and a small particle of antioxidant are added to the ethylene / propylene random polymer, refluxed for 1 hour, and filtered after cooling; the filtrate portion, i.e., the room temperature n-octane soluble fraction, is used to spin dry the solvent with a rotary evaporator, and then the ethylene / propylene random polymer is scraped out, dried, and weighed;

[0010] In the present invention, the boiling heptane insoluble fraction of the ethylene / propylene random polymer is obtained according to the following method: the insoluble part separated from the n-octane fraction in the above text is dried, a certain amount is weighed into a filter paper bag, and extracted with 250 mL of n-heptane (with 3 antioxidants) for 12 hours, and the insoluble matter remaining in the filter paper bag, i.e., the boiling n-heptane insoluble fraction, is dried and weighed;

[0011] In the present invention, the molar amount of ethylene in the boiling heptane insoluble fraction and the molar content of ethylene in the room temperature octane soluble fraction are both measured by infrared analysis using a 470 FT-IR Fourier transform infrared spectrometer produced by Nicolet Company, USA.

[0012] The second aspect of the present invention provides a catalyst component for preparing the above-mentioned ethylene / propylene random polymer, wherein the catalyst component is a reaction product comprising the following components or the following components:

[0013] (1) magnesium compounds,

[0014] (2) Titanium-containing compounds,

[0015] (3) Internal electron donor compounds;

[0016] 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%.

[0017] According to some embodiments of the present invention, the diol ester compound is selected from the diol ester compound represented by formula (I);

[0018]

[0019] 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 20Alkyl, 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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).

[0024] 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.

[0025] 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 to attach it to the solid, and then the solid is treated with titanium tetrahalide or titanium tetrahalide and an inert diluent.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] The third aspect of the present invention provides a method for synthesizing the above-mentioned ethylene / propylene random polymer, comprising polymerizing ethylene and propylene in one or more reactors, preferably one reactor, in the presence of a catalyst and hydrogen; the catalyst comprises a catalyst component for preparing ethylene / propylene random polymers, an alkyl aluminum compound and an optional external electron donor compound.

[0030] According to some embodiments of the present invention, the polymerization conditions include a molar ratio of ethylene:propylene of 1:(8-10).

[0031] 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.

[0032] According to some embodiments of the present invention, the external electron donor compound is selected from the group consisting of: 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.

[0033] Beneficial effects:

[0034] The ethylene content in the ethylene / propylene random polymer of the present invention is higher in high molecular weight than that of existing polymers, and lower in low molecular weight than that of existing polymers. The obtained polymer has excellent rigidity and toughness, and good rigidity-toughness balance.

[0035] The present invention also provides a method for synthesizing an ethylene / propylene random copolymer. The synthesis of the ethylene / propylene random copolymer can be carried out in one reactor, which makes the operation simpler and more conducive to energy conservation and emission reduction. DETAILED DESCRIPTION

[0036] The present invention will be further described below in conjunction with the embodiments, but the present invention is not limited by these embodiments.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] In the embodiment of the present invention, the room temperature octane soluble fraction is obtained by the following method: add 150 mL of n-octane and a small particle of antioxidant to the polymer, reflux for one hour, cool and filter. The filtrate is the room temperature n-octane soluble fraction, and the solvent is dried by a rotary evaporator, and the polymer is scraped out, dried and weighed;

[0042] In the embodiment of the present invention, the boiling heptane insoluble fraction is obtained by the following method: the insoluble part separated from the n-octane fraction in the above text is dried, a certain amount is weighed into a filter paper bag, and extracted with 250 mL of n-heptane (plus 3 antioxidants) for 12 hours. Finally, the insoluble matter remaining in the filter paper bag, i.e., the boiling n-heptane insoluble fraction, is dried and weighed.

[0043] In the embodiments of the present invention, the molar amount of ethylene in the boiling heptane insoluble fraction and the molar amount of ethylene in the room temperature octane soluble fraction were measured by infrared analysis using a 470 FT-IR Fourier transform infrared spectrometer from Nicolet, USA.

[0044] In the embodiment of the present invention, the test standard for the tensile yield stress, tensile elastic modulus and impact strength (notched impact strength of simply supported beam, 23° C.) of the ethylene / propylene random polymer is GB / T12670-2008.

[0045] 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.

[0046] Example 1

[0047] This embodiment provides a catalyst component for preparing ethylene / propylene random polymer.

[0048] The preparation method is as follows:

[0049] 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 heat 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), heat 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 ethylene / propylene random polymers, wherein the meso content in the catalyst component for preparing ethylene / propylene random polymers is 100%.

[0050] This embodiment further provides a method for synthesizing an ethylene / propylene random polymer.

[0051] In a polymerization bottle with a volume of 1000 mL, polymerization was carried out at normal pressure and a constant temperature of 60°C with magnetic stirring; the steps are as follows:

[0052] Before the polymerization reaction, the main catalyst (the catalyst component for preparing ethylene / propylene random polymer prepared in the above Example 1) was pre-contacted with triethylaluminum (TEA) and an external electron donor in a prepolymerization bottle with a volume of 300 mL. The specific operation method was as follows: 100 mL of heptane was added to the 300 mL prepolymerization bottle, stirring was started at room temperature, TEA and the main catalyst were added according to Al:Ti=10:1 (molar ratio), after stirring for 5 minutes, the external electron donor C-donor (cyclohexylmethyl dihydrogen peroxide) was added according to Si / Ti=5 (molar ratio). After stirring for 5 minutes, all the suspension in the prepolymerization bottle was transferred into a polymerization bottle which was previously added with about 500 mL of n-heptane and into which a saturated ethylene / propylene / hydrogen mixed gas (the molar ratio of ethylene:propylene:hydrogen was 10:88:2) was introduced at a temperature of 60°C, and a polymerization reaction was carried out under stirring to obtain the ethylene / propylene random polymer; during the polymerization reaction, the pressure in the bottle was kept constant by continuously adding gaseous monomers at normal pressure to the polymerization bottle.

[0053] Example 2

[0054] This embodiment provides a catalyst component for preparing ethylene / propylene random polymer.

[0055] The preparation method is the same as that of Example 1, except that the meso content of the catalyst component for preparing ethylene / propylene random polymer is 98.4%.

[0056] This embodiment further provides a method for synthesizing an ethylene / propylene random polymer.

[0057] The steps are the same as in Example 1.

[0058] Example 3

[0059] This embodiment provides a catalyst component for preparing ethylene / propylene random polymer.

[0060] The preparation method is the same as that of Example 1, except that the meso content of the catalyst component for preparing ethylene / propylene random polymer is 96%.

[0061] This embodiment further provides a method for synthesizing an ethylene / propylene random polymer.

[0062] The steps are the same as in Example 1.

[0063] Example 4

[0064] This embodiment provides a catalyst component for preparing ethylene / propylene random polymer.

[0065] The preparation method is the same as that in 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 in the catalyst component for preparing ethylene / propylene random polymer is 100%.

[0066] This embodiment further provides a method for synthesizing an ethylene / propylene random polymer.

[0067] The steps are the same as in Example 1.

[0068] Example 5

[0069] This embodiment provides a catalyst component for preparing ethylene / propylene random polymer.

[0070] The preparation method is the same as that of Example 1.

[0071] This embodiment further provides a method for synthesizing an ethylene / propylene random polymer.

[0072] The steps are the same as those in Example 4, except that the number of reactors (polymerization bottles) is 2.

[0073] Example 6

[0074] This embodiment provides a catalyst component for preparing ethylene / propylene random polymer.

[0075] The preparation method is the same as that in 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 C (2,4-pentanediol dibenzoate), and the meso content in the catalyst component for preparing ethylene / propylene random polymer is 100%.

[0076] This embodiment further provides a method for synthesizing an ethylene / propylene random polymer.

[0077] The steps are the same as in Example 1.

[0078] Example 7

[0079] This embodiment provides a catalyst component for preparing ethylene / propylene random polymer.

[0080] The preparation method is the same as that in 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 D (2,4-pentanediol di-n-propyl benzoate), and the meso content in the catalyst component for preparing ethylene / propylene random polymer is 100%.

[0081] This embodiment further provides a method for synthesizing an ethylene / propylene random polymer.

[0082] The steps are the same as in Example 1.

[0083] Comparative Example 1

[0084] This comparative example provides a catalyst component for preparing ethylene / propylene random polymer.

[0085] The preparation method is the same as that in 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 (9,9-bis(methoxymethyl)fluorene), and the catalyst component for preparing ethylene / propylene random polymer does not contain meso.

[0086] This comparative example further provides a method for synthesizing an ethylene / propylene random polymer.

[0087] The steps are the same as in Example 1.

[0088] Comparative Example 2

[0089] This comparative example provides a catalyst component for preparing ethylene / propylene random polymer.

[0090] The preparation method is the same as that of Comparative Example 1.

[0091] This comparative example further provides a method for synthesizing an ethylene / propylene random polymer.

[0092] The steps are the same as those of Comparative Example 1, except that the number of reactors (polymerization bottles) is 2.

[0093] Comparative Example 3

[0094] This comparative example provides a catalyst component for preparing ethylene / propylene random polymer.

[0095] The preparation method is the same as that in 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 (di-n-butyl phthalate), and the catalyst component for preparing ethylene / propylene random polymer does not contain meso.

[0096] This comparative example further provides a method for synthesizing an ethylene / propylene random polymer.

[0097] The steps are the same as in Example 1.

[0098] Comparative Example 4

[0099] This comparative example provides a catalyst component for preparing ethylene / propylene random polymer.

[0100] The preparation method is the same as that of Example 1, except that the meso content of the catalyst component for preparing ethylene / propylene random polymer is 90%.

[0101] This comparative example further provides a method for synthesizing an ethylene / propylene random polymer.

[0102] The steps are the same as in Example 1.

[0103] Comparative Example 5

[0104] This comparative example provides a catalyst component for preparing ethylene / propylene random polymer.

[0105] The preparation method is the same as Example 1.

[0106] This comparative example further provides a method for synthesizing an ethylene / propylene random polymer.

[0107] The steps are the same as those in Example 1, except that the ethylene / propylene molar ratio is 1:7.

[0108] In order to further illustrate the progress of the present invention, the ethylene / propylene random polymers prepared in the above Examples 1-7 and Comparative Examples 1-5 are now subjected to performance tests, and the test results are statistically shown in the following Table 1;

[0109] Table 1

[0110]

[0111] In Table 1, ethylene content-1 means the molar content of ethylene in the boiling heptane insoluble fraction; ethylene content-2 means the molar content of ethylene in the room temperature octane soluble fraction.

[0112] It can be seen from the results in Table 1 that the ethylene / propylene random polymer synthesized by the catalyst component for preparing ethylene / propylene random polymer prepared by the present invention has high rigidity and high toughness under the conditions of the ethylene molar content of the boiling heptane insoluble fraction and the ethylene molar content of the room temperature octane soluble fraction within the required range, and has a very good rigidity-toughness balance.

[0113] 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. An ethylene / propylene random polymer, characterized in that: The molar amount of ethylene in the boiling heptane insoluble fraction of the ethylene / propylene random polymer is ≧0.5%, and the molar content of ethylene in the room temperature octane soluble fraction is ≦11%.

2. The ethylene / propylene random polymer according to claim 1, characterized in that The molar amount of ethylene in the boiling heptane insoluble fraction of the ethylene / propylene random polymer is ≧1%, and the molar content of ethylene in the room temperature octane soluble fraction is ≦10%.

3. The ethylene / propylene random polymer according to claim 1 or 2, characterized in that The tensile elastic modulus of the ethylene / propylene random polymer is ≥700Mpa, and the simply supported beam impact strength is ≥51KJ / m 2 .

4. The ethylene / propylene random polymer according to claim 3, characterized in that The tensile elastic modulus of the ethylene / propylene random polymer is ≥700Mpa, and the simply supported beam impact strength is ≥55KJ / m 2 .

5. A catalyst component for preparing the ethylene / propylene random polymer according to any one of claims 1 to 4, 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%.

6. The catalyst component according to claim 5, 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.

7. The catalyst component according to claim 5 or 6, 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, 6-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.

8. The catalyst component according to any one of claims 5 to 7, characterized in that 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 molecular formula of magnesium dihalide is replaced by alkoxy or halogenated alkoxy; 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; And / or, 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.

9. The catalyst component according to any one of claims 5 to 8, characterized in that 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).

10. A method for synthesizing an ethylene / propylene random polymer according to any one of claims 1 to 4, characterized in that: The method comprises polymerizing ethylene and propylene in one or more reactors, preferably one reactor, in the presence of a catalyst and hydrogen; the catalyst comprises a catalyst component for preparing an ethylene / propylene random polymer, an alkyl aluminum compound and an optional external electron donor compound.

11. The synthesis method according to claim 10, characterized in that: The polymerization conditions include a molar ratio of ethylene to propylene of 1:(8-10).

12. The synthesis method according to claim 10 or 11, 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 any one of triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydrogenate, diisobutylaluminum monohydrogenate, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride and ethylaluminum 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.

Images