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CN110903424B - Multiphase propylene copolymer and continuous gas-phase fluidized bed polymerization process thereof - Google Patents

Multiphase propylene copolymer and continuous gas-phase fluidized bed polymerization process thereof Download PDF

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CN110903424B
CN110903424B CN201911330308.1A CN201911330308A CN110903424B CN 110903424 B CN110903424 B CN 110903424B CN 201911330308 A CN201911330308 A CN 201911330308A CN 110903424 B CN110903424 B CN 110903424B
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张庆海
刘鑫
邵永飞
卢振林
刘永志
安宝玉
王宏亮
李先亮
李凤
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Jiutai Energy Jungle Co ltd
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    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract

A heterophasic propylene copolymer is prepared by a continuous gas phase fluidised bed polymerisation process which produces heterophasic propylene copolymers with high ethylene or rubber content without fouling and without the need for reduced yields. The multiphase propylene copolymer obtained by the method has higher ethylene content and rubber component content, and shows excellent impact resistance and balance of rigidity and toughness.

Description

Multiphase propylene copolymer and continuous gas-phase fluidized bed polymerization process thereof
Technical Field
The present invention relates to a process and product for the gas phase polymerisation of propylene, in particular to a continuous gas phase fluidised bed polymerisation process for the preparation of heterophasic propylene copolymers and to the heterophasic propylene copolymers obtained thereby.
Background
Homo-polypropylene exhibits poor impact resistance and flexibility due to its high crystallinity. However, these properties can be significantly improved by blending an ethylene-propylene copolymer elastomer with a crystalline homopolypropylene to give a polyolefin blend known as "heterophasic propylene copolymer".
One method for preparing such heterophasic propylene copolymers is to melt extrude the ethylene-propylene copolymer elastomer with the crystalline homopolypropylene in an extruder or kneader. A disadvantage of this process is that it is particularly difficult to mix the two components in a homogeneous manner, since the melt viscosities of the individual polymer components to be mixed are usually significantly different. In addition, the high temperatures typically required during phase mixing can degrade one of the polymer components.
At present, another commonly used process for the preparation of heterophasic propylene copolymers is called "polymer in situ blending", wherein a semi-crystalline component (propylene homopolymer) is prepared in a first polymerization reactor (liquid phase loop reactor) and the resulting polymer particles are then transferred to a continuous polymerization reactor (gas phase fluidized bed reactor), in which an elastomeric component (e.g. ethylene-propylene copolymer) is produced, thus preparing the polymer blend by sequential polymerization in two or more reactors arranged in series. Thus, during the polymerization stage, mixing of polymer components of different molar mass distribution and/or chemical composition takes place within the polymer particles. For this polymerization process, the polymerization activity of the Ziegler-Natta catalyst is significantly decreased in the second gas-phase copolymerization stage after undergoing rapid release of the polymerization activity in the first liquid-phase homopolymerization stage. Meanwhile, in order to prevent the rubber phase from forming or wrapping on the surface of the polymer particles entering the second reactor, which causes sticky materials, an anti-sticking agent is added in the second polymerization step to inhibit the polymerization activity on the surface of the polymer particles, so that the rubber phase is formed only in the inner pores of the polymer particles. The addition of the anti-sticking agent further reduces the polymerization activity of the gas-phase copolymerization. The rubber phase content in the product is determined by the capacity control of the second polymerization step, namely, the polymerization activity and the residence time of the materials in the reactor, and after the polymerization activity is greatly consumed, the capacity can be controlled only by the residence time of the materials. However, for the existing polymerization production device in China at present, due to the limitation of the design and construction scale of a gas phase reactor, when the material level of a fluidized bed reaches the maximum limit, the retention time of the material in a gas phase copolymerization stage is not long enough, the regulation and control range of the production process is limited, and the rubber phase content of an impact-resistant polypropylene product cannot meet the index requirement easily.
A gas-phase UNIPOL polypropylene production process is a gas-phase olefin polymerization technology widely adopted at present. Due to the self-limitation of the reaction kinetics of the fluidized bed and the low operation pressure, the storage amount of materials in the system is reduced, so that the process is safer than other processes, and the risk of overpressure of equipment when an accident is out of control does not exist. The process has no liquid waste to discharge and has little hydrocarbon emission to the atmosphere, thus having very little environmental impact and being easier to meet various strict regulatory requirements for environmental protection, health and safety than other processes. Owing to the characteristics of this process, it is possible to prepare heterophasic propylene copolymers by continuous gas phase polymerization.
Disclosure of Invention
It is an object of the present invention to provide a process for the continuous gas-phase polymerization of heterophasic propylene copolymers which allows the production of heterophasic propylene copolymers having a high ethylene or rubber content without fouling and without the need to reduce the yield.
It is another object of the present invention to provide a heterophasic propylene copolymer having a high ethylene content, a high rubber content, exhibiting excellent impact properties and a balance of stiffness and toughness.
A process for the continuous gas-phase polymerization of heterophasic propylene copolymers comprising the steps of:
(1) carrying out a polymerization reaction of propylene and a comonomer in the presence of a Ziegler-Natta catalyst in a first gas phase fluidized bed reactor to obtain crystalline polypropylene; the polymerization temperature is from 40 to 130 ℃, preferably from 50 to 90 ℃, particularly preferably from 55 to 75 ℃; the polymerization pressure is from 1.0 to 3.0MPa, preferably from 1.4 to 2.5MPa, particularly preferably from 2.0 to 2.4 MPa; a hydrogen/propylene molar ratio of from 0.05 to 0.30, preferably from 0.08 to 0.2, particularly preferably from 0.10 to 0.15;
(2) introducing a propylene homopolymer into a second gas-phase fluidized bed reactor, and carrying out copolymerization reaction of a comonomer and propylene to obtain a multiphase propylene copolymer;
wherein the polymerization temperature is 50 to 90 ℃, preferably 60 to 80 ℃, particularly preferably 65 to 75 ℃; the polymerization pressure is from 1 to 5MPa, preferably from 1 to 3MPa, particularly preferably from 1.5 to 2.5 MPa; a hydrogen/propylene molar ratio of from 0.01 to 0.30, preferably from 0.01 to 0.2, particularly preferably from 0.02 to 0.05; the molar comonomer/propylene ratio is from 0.50 to 1.20, preferably from 0.6 to 1.00, particularly preferably from 0.70 to 0.90.
In some embodiments, the total amount of alpha-olefin comonomer in the first gas phase fluidized bed reactor should be less than 10 wt%, preferably less than 5 wt%, and particularly preferably less than 3 wt%.
In some embodiments, the volume of propylene monomer in the first gas phase fluidized bed reactor is from 10% to 100%, preferably from 20% to 80%, particularly preferably from 30 to 70% by volume of the total volume of gases in the reactor.
In some embodiments, the molar ratio of alpha-olefin comonomer/propylene in the first gas phase fluidized bed reactor is in the range of from 0.05 to 0.15, preferably from 0.06 to 0.12, particularly preferably from 0.07 to 0.10.
In some embodiments, the comonomer is an alpha-olefin, preferably ethylene, 1-hexene, 1-octene, particularly preferably ethylene.
A heterophasic propylene copolymer having an alpha-olefin comonomer content of from 25 to 40 mol%, preferably from 27 to 38 mol%, particularly preferably from 28 to 35 mol%; a melt flow rate, measured at 230 ℃ under a load of 2.16kg, of from 1.5 to 5g/10min, preferably from 1.6 to 4g/10min, particularly preferably from 1.7 to 2.0g/10 min; the weight average molecular weight (Mw) is 350000-450000g/mol, preferably 380000-420000g/mol, particularly preferably 400000-410000g/mol, and the molecular weight distribution (Mw/Mn) is 6-12, preferably 7-11, particularly preferably 8-10; the RT fraction obtained by temperature rising elution fractionation (TRFE) has a weight percentage of 18 to 30%, preferably 20 to 28%, particularly preferably 22 to 25%; the RT fraction has an ethylene content of 55 to 70 mol%, preferably 58 to 68 mol%, particularly preferably 60 to 66 mol%; the RT fraction is subjected to13Number average sequence length N of propene by C NMRPFrom 1.0 to 5.0, preferably from 1.5 to 4.5, particularly preferably from 2.0 to 4.0; number average sequence length N of ethyleneEIs 2.0 to 5.0, preferably 2.5 to 4.8, particularly preferably 3.0 to 4.5.
In some embodiments, the 60 ℃ fraction obtained by temperature rising elution fractionation (TRFE) has a weight percentage of 6 to 18%, preferably 8 to 16%, particularly preferably 10 to 14%; the ethylene content in the 60 ℃ fraction is from 60 to 70 mol%, preferably from 61 to 68 mol%, particularly preferably from 62 to 66 mol%; n is a radical ofPFrom 1.0 to 5.0, preferably from 1.5 to 4.5, particularly preferably from 2.0 to 4.0; n is a radical ofEFrom 6.0 to 11.0, preferably from 6.5 to 9.5, particularly preferably from 7.0 to 9.0.
In some embodiments, the 90 ℃ fraction obtained by temperature rising elution fractionation (TRFE) comprisesAmounts of 6 to 18%, preferably 8 to 16%, particularly preferably 10 to 14%; the ethylene content in the 90 ℃ fraction is from 58 to 70 mol%, preferably from 60 to 68 mol%, particularly preferably from 62 to 66 mol%; n is a radical ofPFrom 5.0 to 10.0, preferably from 5.5 to 9.5, particularly preferably from 6.0 to 8.0; n is a radical ofEFrom 12.0 to 20.0, preferably from 12.5 to 19.5, particularly preferably from 15.0 to 18.0.
In some embodiments, the 110 ℃ fraction obtained by temperature rising elution fractionation (TRFE) has a weight percentage of 40 to 60%, preferably 42 to 58%, particularly preferably 44 to 56%; the ethylene content in the 110 ℃ fraction is from 0 to 10 mol%, preferably from 2 to 8 mol%, particularly preferably from 4 to 6 mol%; n is a radical ofP250-400, preferably 260-380, and particularly preferably 270-350; n is a radical ofEFrom 0 to 20.0, preferably from 9.5 to 19.5, particularly preferably from 15.0 to 18.0.
In some embodiments, the 135 ℃ fraction obtained by temperature rising elution fractionation (TRFE) is 10 to 25% by weight, preferably 15 to 23% by weight, and particularly preferably 17 to 22% by weight; the ethylene content in the 135 ℃ fraction is from 0 to 7 mol%, preferably from 1 to 5 mol%, particularly preferably from 2 to 3 mol%; n is a radical ofP650, preferably 470, 630, and particularly preferably 490, 550; n is a radical ofEIs 0 to 18.0, preferably 5.5 to 16.5, particularly preferably 11.0 to 15.0.
The invention is characterized in that:
1. by means of a continuous gas-phase fluidized-bed polymerization process, heterophasic propylene copolymers with a high ethylene or rubber content can be produced without fouling and without a need to reduce the yield.
2. The multiphase propylene copolymer obtained by the continuous gas phase fluidized bed polymerization method has higher ethylene content and rubber component content, and shows excellent impact resistance and balance of rigidity and toughness.
3. In the continuous gas-phase fluidized-bed polymerization method, the number average sequence length of propylene in the fractions of 110 ℃ and 135 ℃ is reduced by properly increasing the ethylene content and controlling the number average sequence length of ethylene and propylene in the fractions of 60 ℃ and 90 ℃ in temperature rising elution fractionation (TRFE), so that excellent impact resistance and balance between rigidity and toughness can be obtained.
Detailed Description
Before the present compounds, components, compositions, and/or methods are disclosed and described, it is to be understood that this invention is not limited to particular compounds, components, compositions, reactants, reaction conditions, ligands, or the like, unless otherwise specified, as such can vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
Catalyst system
The polymerization process of the present invention is carried out in the presence of a Ziegler-Natta catalyst. Polymerization catalysts of this type comprise a solid catalytic component containing titanium based on a titanium compound supported on a magnesium halide.
Preferred titanium compounds are compounds of the formula Ti (OR) nX4-n, wherein n is 0 to 4, X is halogen and R is a hydrocarbyl group having 1 to 10 carbon atoms or a COR group. Among them, titanium compounds having at least one Ti-halogen bond are particularly preferred, such as titanium tetrahalides or titanium haloalkoxides. A preferred specific titanium compound is TiCl3、TiCl4、Ti(OBu)4、Ti(OBu)Cl3、Ti(OBu)2Cl2、Ti(OBu)3Cl。
A particularly suitable Ziegler-Natta catalyst for the preparation of heterophasic propylene copolymers is one wherein the titanium compound is supported on MgCl together with an internal electron donor compound2Those catalysts described above. Among the internal electron donor compounds, compounds selected from esters, ethers, amines and ketones, preferably alkyl, cycloalkyl and aryl esters of polycarboxylic acids, such as phthalates, succinates. Particularly preferred electron donors include mono-or di-substituted phthalates, wherein the substituents are linear or branched C1-C10 alkyl, C3-C8 cycloalkyl or aryl, such as diisobutyl phthalate, di-n-butyl phthalate and di-n-octyl phthalate.
The catalyst system comprises, in addition to the solid catalytic component described above, an organoaluminium compound and an external donor compound as cocatalysts.
The organoaluminium compound is preferably an alkylaluminium compound selected from trialkylaluminium compounds such as triethylaluminium, triisobutylaluminium, tri-n-butylaluminium, tri-n-hexylaluminium, tri-n-octylaluminium and the like; it is also possible to use alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides, optionally mixed with said trialkylaluminum compounds.
The molar ratio of the titanium-containing solid catalyst component to the organoaluminum compound is from 1:5 to 500, preferably from 1:20 to 400, particularly preferably from 1:50 to 200.
The external electron donor may be selected from alcohols, glycols, esters, ketones, amines, amides, nitriles, alkoxysilanes and ethers. Preferred external electron donors are organosilicon compounds such as one or more of trimethylmethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, pentyltrimethoxysilane, isopentyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane; at least one of diisopropyldimethoxysilane and diisobutyldimethoxysilane is particularly preferable. The molar ratio of the titanium-containing solid catalyst component to the external electron donor is from 1:0 to 500, preferably from 1:10 to 300, particularly preferably from 1:20 to 200.
In addition to high polymerization activity, the above catalyst systems also exhibit excellent morphological characteristics which make them particularly suitable for the gas-phase polymerization process of the present invention.
First gas-phase fluidized-bed reactor
Propylene and optionally an alpha-olefin comonomer are polymerized in a first gas phase fluidized bed reactor to obtain crystalline polypropylene, wherein the catalyst system and a gas mixture comprising propylene, optionally comonomer, hydrogen as molecular weight regulator and inert gas are fed to the gas phase reactor and polymerized to obtain the crystalline polypropylene component. The total amount of comonomer incorporated in the crystalline polypropylene should be less than 10% by weight, preferably less than 5% by weight, particularly preferably less than 3% by weight. The comonomer is an alpha-olefin, preferably ethylene, 1-hexene, 1-octene, particularly preferably ethylene.
The polymerization temperature is from 40 to 130 ℃, preferably from 50 to 90 ℃, particularly preferably from 55 to 75 ℃; the polymerization pressure is from 1.0 to 3.0MPa, preferably from 1.4 to 2.5MPa, particularly preferably from 2.0 to 2.4 MPa.
The hydrogen/propylene molar ratio is from 0.05 to 0.30, preferably from 0.08 to 0.2, particularly preferably from 0.10 to 0.15, the propylene monomer volume being from 10 to 100%, preferably from 20 to 80%, particularly preferably from 30 to 70%, by volume of the total volume of gases in the reactor. The remainder of the feed mixture comprises inert gas and optionally one or more alpha-olefin comonomers. The molar comonomer/propylene ratio is from 0.05 to 0.15, preferably from 0.06 to 0.12, particularly preferably from 0.07 to 0.10.
The inert gas used to diffuse the heat generated by the polymerization reaction is suitably selected from nitrogen or saturated light hydrocarbons, preferably nitrogen or propane.
Second gas-phase fluidized-bed reactor
The catalyst-containing crystalline polypropylene discharged from the first gas-phase fluidized-bed reactor is transferred to the second gas-phase fluidized-bed reactor. In order to prevent the gas mixture discharged from the first reactor from entering the second gas-phase fluidized-bed reactor, the polymer powder is generally passed through a solid/gas separation step to separate the gas mixture and recycle the gas back to the first gas-phase fluidized-bed reactor, while the polymer particles are fed to the second gas-phase fluidized-bed reactor. The comonomer in the second gas phase fluidized bed reactor is an alpha-olefin comonomer, preferred comonomers are ethylene, 1-hexene, 1-octene, particularly preferred is ethylene.
The polymerization temperature of the second gas-phase fluidized-bed reactor is from 50 to 90 deg.C, preferably from 60 to 80 deg.C, particularly preferably from 65 to 75 deg.C.
The polymerization pressure is from 1 to 5MPa, preferably from 1 to 3MPa, particularly preferably from 1.5 to 2.5 MPa.
The hydrogen/propylene molar ratio is from 0.01 to 0.30, preferably from 0.01 to 0.2, particularly preferably from 0.02 to 0.05.
The molar comonomer/propylene ratio is from 0.50 to 1.20, preferably from 0.6 to 1.00, particularly preferably from 0.70 to 0.90.
Heterophasic propylene copolymer
The heterophasic propylene copolymers obtainable by the continuous gas phase polymerization of the present invention have a melt flow rate, measured at 230 ℃ under a load of 2.16kg, of from 1.5 to 5g/10min, preferably from 1.6 to 4g/10min, particularly preferably from 1.7 to 2.0g/10 min.
The comonomer content is from 25 to 40 mol%, preferably from 27 to 38 mol%, particularly preferably from 28 to 35 mol%.
The weight average molecular weight (Mw) is 350000-450000g/mol, preferably 380000-420000g/mol, particularly preferably 400000-410000g/mol, and the molecular weight distribution (Mw/Mn) is 6-12, preferably 7-11, particularly preferably 8-10.
The multiphase propylene copolymer prepared by the invention is subjected to temperature rise elution classification, and the classification method comprises the following steps: 15-20 grams of polymer was dissolved in 2 liters of 1, 2, 4-trichlorobenzene at 135 ℃ for 4 hours with stirring, and the polymer solution was forced through 15psig (100kPa) nitrogen to a steel pipe column packed with 50-60 mesh spherical technical quality glass beads. The steel pipe column was immersed in a thermal control oil jacket initially set at 140 ℃. After the polymer solution was completely filled, it was slowly cooled to room temperature at 1 ℃/min and maintained for 24 hours. Pumping pure 1, 2, 4-trichlorobenzene into the steel pipe column, pumping out the solution in which the room-temperature soluble polymer is dissolved, heating to 60 ℃ and staying for 6 hours, pumping pure 1, 2, 4-trichlorobenzene into the steel pipe column, and pumping out the solution in which the 60- ℃ soluble polymer is dissolved; the above procedure was then repeated, collecting the corresponding polymer solutions at 90, 110 and 135 ℃ in sequence. The polymer solution obtained in each case was precipitated with 2 volumes of acetone, filtered and washed to give the corresponding fractions at RT (room temperature), 60, 90, 110 and 135 ℃ respectively.
Taking 70-75 mg of sample for each fraction, dissolving in 0.5mL of deuterated o-dichlorobenzene at 125 ℃, and measuring the sample at 140 ℃ by using a Varian Unity 400MHz type nuclear magnetic resonance apparatus13C NMR spectrum. Calculating the number average sequence length N using a spectrogramPAnd NEIn which N isP＝(PP+0.5PE)/0.5PE，NE＝(EE+0.5PE)/0.5PE。
The weight percentage content of the RT fraction, based on 100% by weight of the heterophasic propylene copolymer, is from 18 to 30%, preferably from 20 to 28%, particularly preferably from 22 to 25%;wherein the ethylene content is from 55 to 70 mol%, preferably from 58 to 68 mol%, particularly preferably from 60 to 66 mol%; n is a radical ofPFrom 1.0 to 5.0, preferably from 1.5 to 4.5, particularly preferably from 2.0 to 4.0; n is a radical ofEIs 2.0 to 5.0, preferably 2.5 to 4.8, particularly preferably 3.0 to 4.5.
The weight percentage of the fraction at 60 ℃ is 6-18%, preferably 8-16%, particularly preferably 10-14%, based on 100% by weight of the heterophasic propylene copolymer; wherein the ethylene content is from 60 to 70 mol%, preferably from 61 to 68 mol%, particularly preferably from 62 to 66 mol%; n is a radical ofPFrom 1.0 to 5.0, preferably from 1.5 to 4.5, particularly preferably from 2.0 to 4.0; n is a radical ofEFrom 6.0 to 11.0, preferably from 6.5 to 9.5, particularly preferably from 7.0 to 9.0.
The fraction at 90 ℃ is in a weight percentage, based on 100% by weight of the heterophasic propylene copolymer, of from 6 to 18%, preferably from 8 to 16%, particularly preferably from 10 to 14%; wherein the ethylene content is from 58 to 70 mol%, preferably from 60 to 68 mol%, particularly preferably from 62 to 66 mol%; n is a radical ofPFrom 5.0 to 10.0, preferably from 5.5 to 9.5, particularly preferably from 6.0 to 8.0; n is a radical ofEFrom 12.0 to 20.0, preferably from 12.5 to 19.5, particularly preferably from 15.0 to 18.0.
The proportion by weight of the 110 ℃ fraction is from 40 to 60%, preferably from 42 to 58%, particularly preferably from 44 to 56%, based on 100% by weight of the heterophasic propylene copolymer; wherein the ethylene content is from 0 to 10 mol%, preferably from 2 to 8 mol%, particularly preferably from 4 to 6 mol%; n is a radical ofP250-400, preferably 260-380, and particularly preferably 270-350; n is a radical ofEFrom 0 to 20.0, preferably from 9.5 to 19.5, particularly preferably from 15.0 to 18.0.
The weight percentage of the 135 ℃ fraction is from 10 to 25%, preferably from 15 to 23%, particularly preferably from 17 to 22%, based on 100% by weight of the heterophasic propylene copolymer; wherein the ethylene content is from 0 to 7 mol%, preferably from 1 to 5 mol%, particularly preferably from 2 to 3 mol%; n is a radical ofP650, preferably 470, 630, and particularly preferably 490, 550; n is a radical ofEIs 0 to 18.0, preferably 5.5 to 16.5, particularly preferably 11.0 to 15.0.
The technical solution of the present invention will be described in detail with reference to specific examples.
Examples
In the titanium-containing solid catalytic component used in the examples, Ti is 2.6 wt%, Mg is 17.0 wt%, and internal electron donor dibutyl phthalate is 15.2 wt%. Adding a titanium-containing solid catalytic component, triethyl aluminum, an external electron donor of diisopropyl dimethoxysilane, propylene and optional ethylene into a first gas-phase fluidized bed reactor to carry out polymerization reaction. Wherein, the feeding amount of the titanium-containing solid catalytic component is 0.66g/hr, Al/Ti (mol/mol) ═ 168.33, Al/Si (mol/mol) ═ 6.21; the material level of the reactor is 90 percent, and the polymerization time is 90 minutes, so that a crystalline propylene polymer is obtained;
in a second gas phase fluidized bed reactor, ethylene and propylene are fed in the presence of the crystalline propylene polymer to effect polymerization. 45% of the reactor level and a polymerization time of 50 minutes gave a heterophasic propylene copolymer. Specific process conditions are shown in table 1.
Figure BDA0002329391630000071
TABLE 2 Properties of the polymers obtained in the examples
Figure BDA0002329391630000072
Figure BDA0002329391630000081
Note: the 135 ℃ fraction in example 1 is a propylene homopolymer, the N not being calculatedPAnd NE。
TABLE 3 Properties of the polymers obtained in the examples
Figure BDA0002329391630000082
Figure BDA0002329391630000091

Claims (5)

1. A heterophasic propylene copolymer having a comonomer ethylene content of 28 to 35 mol%; a melt flow rate of 1.7-2.0g/10min measured at 230 ℃ under a load of 2.16 kg; the weight average molecular weight (Mw) is 400000-; the method is characterized in that:
the weight percentage content of RT fraction obtained by heating elution fractionation (TRFE) is 22-25%; the content of ethylene in the RT fraction is 60-66 mol%; the RT fraction has a number average sequence length NP of propylene, measured by 13C NMR, of 1.5 to 4.5; the ethylene number average sequence length NE is 3.0-4.5.
2. The copolymer of claim 1, wherein the 60 ℃ fraction obtained by temperature rising elution fractionation (TRFE) is 10 to 14% by weight; the ethylene content in the 60 ℃ fraction is from 62 to 66 mol%; NP is 2.0-4.0; NE is 7.0-9.0.
3. The copolymer of claim 1, wherein the 90 ℃ fraction obtained by temperature rising elution fractionation (TRFE) is 10 to 14% by weight; the ethylene content in the 90 ℃ fraction is 62-66 mol%; NP is 6.0-8.0; NE is 15.0-18.0.
4. The copolymer of claim 1, wherein the 110 ℃ fraction obtained by temperature rising elution fractionation (TRFE) is 44 to 56% by weight; the ethylene content in the 110 ℃ fraction is 4-6 mol%; NP is 270-; NE is 15.0-18.0.
5. The copolymer of claim 1, wherein the 135 ℃ fraction obtained by temperature rising elution fractionation (TRFE) is 10 to 25% by weight; the ethylene content in the 135 ℃ fraction is 0-7 mol%; NP is 490-550; NE is 0-18.0.
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