Terpolymer with wide molecular weight distribution and high melt strength as well as preparation method and application thereof

Abstract

The invention provides an ethylene-propylene-butylene terpolymer with wide molecular weight distribution and high melt strength as well as a preparation method and application thereof, and belongs to the technical field of olefin polymerization. A specific catalyst component containing cyanic acid ester and diol ester internal electron donor compounds is used, a silane external electron donor compound is added, the cyanic acid ester external electron donor compound and a diol ester external electron donor are compounded for use, a unique catalyst system is formed, a specific preparation process is matched, and the specific catalyst component is used for preparing the catalyst. The ethylene-propylene-butylene terpolymer has wide molecular weight distribution and high proportion of supermolecules. The method provided by the invention is simple, is easy for industrial production, can be used for preparing high-performance products, and has a wide application prospect.

Description

Technical Field

[0001] The invention relates to a terpolymer with wide molecular weight distribution and high melt strength, and a preparation method and application thereof, belonging to the technical field of olefin polymerization. Background Art

[0002] Polypropylene is one of the most important general-purpose plastics. However, the semi-crystalline conventional linear isotactic polypropylene (iPP) has low melt strength, is difficult to process by thermoforming, and has limited application areas. High melt strength polypropylene (HMSPP) refers to the requirement of a higher tensile force when the melt is stretched and broken. Improving the melt strength of general-purpose polypropylene has always been a hot topic in this field of research, and it is also a technical bottleneck for the expansion of polypropylene application areas and high performance. With its high melt strength, yield strength, bending modulus, heat deformation temperature, melting point, crystallization temperature and short crystallization time, high melt strength polypropylene has been widely used in thermoforming, foaming, extrusion coating and other fields. In these applications, high melt strength polypropylene is used in thermoforming processing to enable the parts to be demolded at a higher temperature, shorten the molding cycle, and increase production; during the foaming process, it can resist the rupture of the micropore wall, increase the foaming ratio, reduce the density, and increase the closed cell rate; during the extrusion coating process, it exhibits a faster coating speed and very small necking. Therefore, high melt strength polypropylene is the research focus of polypropylene production technology innovation.

[0003] At present, reaction extrusion, polymerization technology and irradiation modification are the main methods used to improve the melt strength of polypropylene. The reaction extrusion method prepares high melt strength polypropylene by adding peroxide and other multifunctional reaction monomers to polypropylene. That is, peroxide and a third monomer are added to the polypropylene powder, and long-chain branched polypropylene is generated after the reaction, thereby improving the melt strength of polypropylene. The reaction extrusion method must add a variety of chemical components to produce high melt strength polypropylene, which increases the production cost on the one hand, and also causes fluctuations in product quality due to the control of the amount added. More importantly, the long-term presence of additives in the polymer will lead to a gradual deterioration of the yellow index and physical properties of the product. Some added compounds are still toxic and cannot be used for contact with food and medicine. Many research institutions at home and abroad use this method to produce high melt strength polypropylene with a long-chain branched structure.

[0004] The polymerization technology currently includes one-step method, two-step method, copolymerization method and in-situ polymerization method. The foreign patent technology is based on Chisso's US 6225432B1 using CGC (constrained geometry catalysts) constrained geometry catalysts to branch the polymer long chain; Chinese invention patents CN200710179266.7 and CN 201010147765.X respectively graft copolymerize propylene with α, ω-non-conjugated diene, styrene and substituted styrene monomers (T-type monomers) to form long chain branches. The polymerization technology method can accurately control the length of the branch chain and the distribution of the branch structure in the polymer main chain. In the industry of preparing high melt strength polypropylene with Ziegler-Natta catalyst, other monomers are introduced, or more reactors are added while changing the types of materials in different reactors, which increases the reaction raw materials, increases the processing steps such as recovery and purification, and the process is cumbersome. The practicality of constructing long chain branched structures based on metallocene catalyst systems currently needs to be improved.

[0005] Irradiation modification is to select appropriate radiation sources and doses to irradiate polypropylene, so that the polypropylene molecular chains are cross-linked to produce long branched structures, thereby improving the melt strength of polypropylene. In terms of the selection of radiation sources, electron rays generated by electron accelerators or gamma rays generated by 60Co are currently mainly used.

[0006] Therefore, it is very necessary to develop an economical, environmentally friendly, convenient and high-performance high melt strength polypropylene production technology. Among them, the catalyst in-situ generation method is the most applicable, environmentally friendly, simple and most stable industrial production method. This method is to prepare a wide molecular weight distribution polypropylene by using a reactor with a specific catalyst to achieve high melt strength of the final polymer. Summary of the invention

[0007] In order to solve the deficiencies in the prior art, the present invention provides a method and application of preparing a terpolymer with wide molecular weight distribution and high melt strength through systematic research. The present invention adopts a Ziegler-Natta catalyst component containing internal electron donors such as cyanoesters and diol esters and / or other types of compounds. When forming the catalyst, a unique catalyst system is formed by a reasonable compounding of three different types of external electron donors, namely silanes, cyanoesters and diol esters. The method of direct polymerization in the reactor obtains a terpolymer with wide molecular weight distribution and high melt strength. z+1 / M n The ethylene-propylene-butylene terpolymer has a molecular weight distribution and contains a large number of ultra-high molecular weight fractions. The polymer has very high melt strength.

[0008] The present invention provides an ethylene-propylene-butylene terpolymer with a wide molecular weight distribution and high melt strength, wherein the molecular weight distribution M of the ethylene-propylene-butylene terpolymer is z+1 / Mn It is 60 to 150.

[0009] Optionally, the melt strength of the ethylene-propylene-butylene terpolymer is 0.20-0.85N.

[0010] The present invention also provides a method for preparing an ethylene-propylene-butene terpolymer with a wide molecular weight distribution and high melt strength, wherein ethylene, propylene and butene are contacted with a catalyst system under olefin polymerization conditions to react and generate the ethylene-propylene-butene terpolymer;

[0011] The catalyst system comprises the following components and reaction products thereof:

[0012] A, a catalyst component; the catalyst component comprises titanium, a cyanoester internal electron donor compound and a diol ester internal electron donor compound;

[0013] B. Organoaluminum compounds;

[0014] C. External electron donor compounds; the external electron donor compounds include silane external electron donor compounds, cyanate external electron donor compounds and glycol ester external electron donor compounds.

[0015] Optionally, the catalyst component, the organoaluminum compound and the external electron donor compound are pre-contacted before contacting ethylene, propylene and butene; the pre-contact time is 0.1 to 60 minutes, preferably 1 to 40 minutes; the pre-contact temperature is -20°C to 80°C, preferably 0°C to 60°C.

[0016] Optionally, the catalyst component, the organoaluminum compound and the silane external electron donor compound are first pre-contacted, then pre-contacted with the cyanate external electron donor compound, and then pre-contacted with the glycol ester external electron donor compound.

[0017] Optionally, the catalyst system is first prepolymerized to a certain extent in the presence of a small amount of ethylene, propylene and butene to obtain a prepolymerized catalyst, and then the prepolymerized catalyst is further contacted with ethylene, propylene and butene to react to obtain an ethylene-propylene-butene terpolymer; the prepolymerization ratio is 1 to 1000 g polymer / g catalyst, preferably 2 to 500 g polymer / g catalyst; the prepolymerization temperature is -20°C to 80°C, preferably 0°C to 50°C.

[0018] Optionally, the polymerization conditions include: polymerization temperature of 0°C to 100°C, preferably 30°C to 90°C, and time of 20 to 600 min, preferably 30 to 500 min.

[0019] Optionally, the Ziegler-Natta catalyst component in which the internal electron donor used in the present invention comprises a cyanate ester and a diol ester, based on the total weight of the catalyst component, contains 1.0 wt% to 5.0 wt% of titanium element, 0.5 wt% to 10.0 wt% of a diol ester internal electron donor compound, 3.0 wt% to 20.0 wt% of a cyanate ester internal electron donor compound, and the molar ratio of the diol ester internal electron donor compound to the cyanate ester internal electron donor compound is 0.025:1 to 0.8:1; preferably, based on the total weight of the catalyst component, contains 1.3 wt% to 4.0 wt% of titanium element, 0.8 wt% to 6 wt% of a diol ester internal electron donor compound, 5 wt% to 15 wt% of a cyanate ester internal electron donor compound, and the molar ratio of the diol ester internal electron donor compound to the cyanate internal electron donor compound is (0.05 to 0.6):1.

[0020] Optionally, the cyanoester internal electron donor compound has a structure shown in general formula (I):

[0021]

[0022] In the general formula (I), R 1 and R 2 The groups are independently selected from linear C1-C4 alkyl groups and branched C1-C4 alkyl groups; R 3 and R 4 Independently selected from C3-C6 isoalkyl, C3-C6 secondary alkyl and C3-C6 cycloalkyl.

[0023] Optionally, the cyano ester internal electron donor compound is selected from cyanosuccinate compounds, preferably 2,3-dinon-linear alkyl-2-cyanosuccinate diester compounds, more preferably 2,3-diisopropyl-2-dicyanosuccinic acid dimethyl ester, 2,3-diisopropyl-2-dicyanosuccinic acid diethyl ester, 2,3-diisopropyl-2-dicyanosuccinic acid di-n-propyl ester, 2,3-diisopropyl-2-dicyanosuccinic acid di-isopropyl ester, 2,3-diisopropyl-2-dicyanosuccinic acid di-n-butyl ester, 2,3-diisopropyl-2-dicyanosuccinic acid di-isobutyl ester, 2,3-diisopropyl-2-dicyanosuccinic acid-1-methyl-4-ethyl ester (R 1 = methyl, R 2 =ethyl), 2,3-diisopropyl-2-cyanosuccinic acid-1-ethyl ester-4-methyl ester (R 1 =Ethyl, R 2 = methyl), 2,3-diisopropyl-2-cyanosuccinic acid-1-n-butyl-4-ethyl ester (R 1 = n-butyl, R 2=ethyl), 2,3-diisopropyl-2-cyanosuccinic acid-1-ethyl ester-4-n-butyl ester (R 1 =Ethyl, R 2 =n-butyl), dimethyl 2,3-diisobutyl-2-dicyanosuccinate, diethyl 2,3-diisobutyl-2-dicyanosuccinate, di-n-propyl 2,3-diisobutyl-2-dicyanosuccinate, diisopropyl 2,3-diisobutyl-2-dicyanosuccinate, di-n-butyl 2,3-diisobutyl-2-dicyanosuccinate, diisobutyl 2,3-diisobutyl-2-dicyanosuccinate, 1-methyl-4-ethyl 2,3-diisobutyl-2-cyanosuccinate (R 1 = methyl, R 2 =ethyl), 2,3-diisobutyl-2-cyanosuccinic acid-1-ethyl ester-4-methyl ester (R 1 =Ethyl, R 2 = methyl), 2,3-diisobutyl-2-cyanosuccinic acid-1-n-butyl-4-ethyl ester (R 1 = n-butyl, R 2 =ethyl), 2,3-diisobutyl-2-cyanosuccinic acid-1-ethyl ester-4-n-butyl ester (R 1 =Ethyl, R 2 =n-butyl), dimethyl 2,3-di-sec-butyl-2-dicyanosuccinate, diethyl 2,3-di-sec-butyl-2-dicyanosuccinate, di-n-propyl 2,3-di-sec-butyl-2-dicyanosuccinate, diisopropyl 2,3-di-sec-butyl-2-dicyanosuccinate, di-n-butyl 2,3-di-sec-butyl-2-dicyanosuccinate, diisobutyl 2,3-di-sec-butyl-2-dicyanosuccinate, 1-methyl-4-ethyl 2,3-di-sec-butyl-2-cyanosuccinate (R 1 = methyl, R 2 =ethyl), 2,3-di-sec-butyl-2-cyanosuccinic acid-1-ethyl-4-methyl ester (R 1 =Ethyl, R 2 = methyl), 2,3-di-sec-butyl-2-cyanosuccinic acid-1-n-butyl-4-ethyl ester (R 1 = n-butyl, R 2 =ethyl), 2,3-di-sec-butyl-2-cyanosuccinic acid-1-ethyl ester-4-n-butyl ester (R 1 =Ethyl, R 2=n-butyl), dimethyl 2,3-dicyclopentyl-2-dicyanosuccinate, diethyl 2,3-dicyclopentyl-2-dicyanosuccinate, di-n-propyl 2,3-dicyclopentyl-2-dicyanosuccinate, diisopropyl 2,3-dicyclopentyl-2-dicyanosuccinate, di-n-butyl 2,3-dicyclopentyl-2-dicyanosuccinate, diisobutyl 2,3-dicyclopentyl-2-dicyanosuccinate, 1-methyl-4-ethyl 2,3-dicyclopentyl-2-cyanosuccinate (R 1 = methyl, R 2 =ethyl), 2,3-dicyclopentyl-2-cyanosuccinic acid-1-ethyl ester-4-methyl ester (R 1 =Ethyl, R 2 = methyl), 2,3-dicyclopentyl-2-cyanosuccinic acid-1-n-butyl-4-ethyl ester (R 1 = n-butyl, R 2 =ethyl), 2,3-dicyclopentyl-2-cyanosuccinic acid-1-ethyl ester-4-n-butyl ester (R 1 =Ethyl, R 2 =n-butyl), dimethyl 2,3-dicyclohexyl-2-dicyanosuccinate, diethyl 2,3-dicyclohexyl-2-dicyanosuccinate, di-n-propyl 2,3-dicyclohexyl-2-dicyanosuccinate, diisopropyl 2,3-dicyclohexyl-2-dicyanosuccinate, di-n-butyl 2,3-dicyclohexyl-2-dicyanosuccinate, diisobutyl 2,3-dicyclohexyl-2-dicyanosuccinate, 1-methyl-4-ethyl 2,3-dicyclohexyl-2-cyanosuccinate (R 1 = methyl, R 2 =ethyl), 2,3-dicyclohexyl-2-cyanosuccinic acid-1-ethyl ester-4-methyl ester (R 1 =Ethyl, R 2 = methyl), 2,3-dicyclohexyl-2-cyanosuccinic acid-1-n-butyl-4-ethyl ester (R 1 = n-butyl, R 2 =ethyl), 2,3-dicyclohexyl-2-cyanosuccinic acid-1-ethyl ester-4-n-butyl ester (R 1 =Ethyl, R 2 =n-butyl). Among them, at least one of 2,3-diisopropyl-2-dicyanosuccinate diethyl ester, 2,3-diisopropyl-2-dicyanosuccinate di-n-propyl ester, 2,3-diisopropyl-2-dicyanosuccinate diisopropyl ester, 2,3-diisopropyl-2-dicyanosuccinate di-n-butyl ester, and 2,3-diisopropyl-2-dicyanosuccinate diisobutyl ester is further preferred. The above internal electron donor compounds can be used alone or in combination.

[0024] Optionally, in the present invention, the 2,3-dinon-linear alkyl-2-cyanosuccinic acid diester compound is prepared according to the method disclosed in International Patent Application No. PCT / CN2010 / 000202.

[0025] Optionally, the diol ester internal electron donor compound has a structure shown in general formula (II):

[0026]

[0027] In the general formula (II), R1 to R6, R 1 ~R 2n The groups are independently selected from hydrogen, halogen, substituted or unsubstituted straight or branched C1-C 20 Alkyl, substituted or unsubstituted C3~C 20 Cycloalkyl, substituted or unsubstituted C6~C 20 Aryl, substituted or unsubstituted C7~C 20 Alkyl, substituted or unsubstituted C7~C 20 Arylalkyl, substituted or unsubstituted C2~C 10 Alkenyl, substituted or unsubstituted C 10 ~C 20 Condensed ring aromatic or substituted or unsubstituted C 10 ~C 20 Ester group.

[0028] Optionally, in the general formula (II), R1 and R2 are not hydrogen, R3 to R6 and R 1 ~R 2n Any one of the groups optionally contains one or more heteroatoms as a substitute for a carbon atom or a hydrogen atom or both, wherein the heteroatoms are selected from nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atoms, R3 to R6 and R 1 ~R 2n One or more of the groups may optionally form a ring with each other, and n is an integer of 0 to 10.

[0029] Among the compounds represented by the above general formula (II), preferably included are compounds represented by the general formula (III):

[0030]

[0031] In the general formula (III), R1 to R6, R 1 ~R 2 independently selected from hydrogen, halogen atoms, straight or branched C1-C 20 Alkyl, C3~C 20 Cycloalkyl, C6~C 20 Aryl, C7~C 20 Alkyl or C7~C 20 Aralkyl.

[0032] Among the above solid catalyst components of the present invention, the internal electron donor compound is disclosed in Chinese Patents CN1436766A and CN1436796A, and the relevant content disclosed in these patents is incorporated herein by reference in its entirety.

[0033] Optionally, the compounds represented by the general formula (III) include 2-ethyl-1,3-propanediol dibenzoate, 2-propyl-1,3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzoate, 1,3-butanediol dimethylbenzoate, 2-methyl-1,3-butanediol dichlorobenzoate, 2,3-dimethyl-1,3-butanediol dibenzoate, 1,3-pentanediol neopentanoate, 2,4-pentanediol dibenzoate, 2-methyl-1,3-pentanediol benzoate cinnamate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2,4-heptanediol dibenzoate, 2-methyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, etc. Preferably, they are 2,4-pentanediol dibenzoate and 4-ethyl-3,5-heptanediol dibenzoate.

[0034] Optionally, the general formula of the organoaluminum compound is AlR n X 3-n , where R is hydrogen, a hydrocarbon group with 1 to 20 carbon atoms, X is a halogen, and n is an integer of 0 < n ≤ 3.

[0035] Optionally, the organoaluminum compound is selected from alkylaluminum halides such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, monochlorodiethylaluminum, monochlorodiisobutylaluminum, dichloroethylaluminum, etc. Among them, triethylaluminum and triisobutylaluminum are preferred.

[0036] Optionally, the ratio between the organoaluminum compound and the catalyst component is 5 to 5000 in terms of the molar ratio of aluminum element to titanium element, and preferably 20 to 500.

[0037] Optionally, the silane external electron donor compound is selected from at least one of the compounds represented by the general formula R1R2 m Si(OR3) 3-m , R4 n Si(OR5) 4-n and R6R7Si(OR8)2, or a mixture of any two or more of them in any proportion, where m and n are independently integers of 0 to 2; R1 and R2 are the same or different C1 to C 10 linear or branched or cyclic aliphatic groups; R3, R4, R5, R6, and R8 are the same or different C1 to C3 linear aliphatic groups; R7 is a C3 to C6 branched or cyclic aliphatic group.

[0038] Optionally, specific examples of the silane-based external electron donor compound include but are not limited to tetramethoxysilane, n-propyltriethoxysilane, isobutyltriethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, n-propyltrimethoxysilane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisobutyldimethoxysilane, methylcyclohexyldimethoxysilane, methylisobutyldimethoxysilane, dicyclohexyldimethoxysilane, phenyltrimethoxysilane, dicyclopentyldimethoxysilane, and the like.

[0039] Optionally, the molar ratio of the organoaluminum compound to the silane external electron donor is 0.5:1 to 200:1, preferably 1:1 to 100:1, based on the molar ratio of aluminum element to silicon element.

[0040] Optionally, the cyanoester external electron donor compound has a structure shown in general formula (I):

[0041]

[0042] In the general formula (I), R 1 and R 2 The groups are independently selected from linear C1-C4 alkyl groups and branched C1-C4 alkyl groups; R 3 and R 4 Independently selected from C3-C6 isoalkyl, C3-C6 secondary alkyl and C3-C6 cycloalkyl.

[0043] Optionally, the cyano ester external electron donor compound is selected from cyanosuccinate compounds, preferably 2,3-dinon-linear alkyl-2-cyanosuccinate diester compounds, and further preferably 2,3-diisopropyl-2-dicyanosuccinic acid dimethyl ester, 2,3-diisopropyl-2-dicyanosuccinic acid diethyl ester, 2,3-diisopropyl-2-dicyanosuccinic acid di-n-propyl ester, 2,3-diisopropyl-2-dicyanosuccinic acid di-isopropyl ester, 2,3-diisopropyl-2-dicyanosuccinic acid di-n-butyl ester, 2,3-diisopropyl-2-dicyanosuccinic acid di-isobutyl ester, 2,3-diisopropyl-2-dicyanosuccinic acid-1-methyl-4-ethyl ester (R 1 = methyl, R 2 =ethyl), 2,3-diisopropyl-2-cyanosuccinic acid-1-ethyl ester-4-methyl ester (R 1 =Ethyl, R 2 = methyl), 2,3-diisopropyl-2-cyanosuccinic acid-1-n-butyl-4-ethyl ester (R 1 = n-butyl, R 2 =ethyl), 2,3-diisopropyl-2-cyanosuccinic acid-1-ethyl ester-4-n-butyl ester (R1 =Ethyl, R 2 =n-butyl), dimethyl 2,3-diisobutyl-2-dicyanosuccinate, diethyl 2,3-diisobutyl-2-dicyanosuccinate, di-n-propyl 2,3-diisobutyl-2-dicyanosuccinate, diisopropyl 2,3-diisobutyl-2-dicyanosuccinate, di-n-butyl 2,3-diisobutyl-2-dicyanosuccinate, diisobutyl 2,3-diisobutyl-2-dicyanosuccinate, 1-methyl-4-ethyl 2,3-diisobutyl-2-cyanosuccinate (R 1 = methyl, R 2 =ethyl), 2,3-diisobutyl-2-cyanosuccinic acid-1-ethyl ester-4-methyl ester (R 1 =Ethyl, R 2 = methyl), 2,3-diisobutyl-2-cyanosuccinic acid-1-n-butyl-4-ethyl ester (R 1 = n-butyl, R 2 =ethyl), 2,3-diisobutyl-2-cyanosuccinic acid-1-ethyl ester-4-n-butyl ester (R 1 =Ethyl, R 2 =n-butyl), dimethyl 2,3-di-sec-butyl-2-dicyanosuccinate, diethyl 2,3-di-sec-butyl-2-dicyanosuccinate, di-n-propyl 2,3-di-sec-butyl-2-dicyanosuccinate, diisopropyl 2,3-di-sec-butyl-2-dicyanosuccinate, di-n-butyl 2,3-di-sec-butyl-2-dicyanosuccinate, diisobutyl 2,3-di-sec-butyl-2-dicyanosuccinate, 1-methyl-4-ethyl 2,3-di-sec-butyl-2-cyanosuccinate (R 1 = methyl, R 2 =ethyl), 2,3-di-sec-butyl-2-cyanosuccinic acid-1-ethyl-4-methyl ester (R 1 =Ethyl, R 2 = methyl), 2,3-di-sec-butyl-2-cyanosuccinic acid-1-n-butyl-4-ethyl ester (R 1 = n-butyl, R 2 =ethyl), 2,3-di-sec-butyl-2-cyanosuccinic acid-1-ethyl ester-4-n-butyl ester (R 1 =Ethyl, R 2 =n-butyl), dimethyl 2,3-dicyclopentyl-2-dicyanosuccinate, diethyl 2,3-dicyclopentyl-2-dicyanosuccinate, di-n-propyl 2,3-dicyclopentyl-2-dicyanosuccinate, diisopropyl 2,3-dicyclopentyl-2-dicyanosuccinate, di-n-butyl 2,3-dicyclopentyl-2-dicyanosuccinate, diisobutyl 2,3-dicyclopentyl-2-dicyanosuccinate, 1-methyl-4-ethyl 2,3-dicyclopentyl-2-cyanosuccinate (R 1 = methyl, R2 =ethyl), 2,3-dicyclopentyl-2-cyanosuccinic acid-1-ethyl ester-4-methyl ester (R 1 =Ethyl, R 2 = methyl), 2,3-dicyclopentyl-2-cyanosuccinic acid-1-n-butyl-4-ethyl ester (R 1 = n-butyl, R 2 =ethyl), 2,3-dicyclopentyl-2-cyanosuccinic acid-1-ethyl ester-4-n-butyl ester (R 1 =Ethyl, R 2 =n-butyl), dimethyl 2,3-dicyclohexyl-2-dicyanosuccinate, diethyl 2,3-dicyclohexyl-2-dicyanosuccinate, di-n-propyl 2,3-dicyclohexyl-2-dicyanosuccinate, diisopropyl 2,3-dicyclohexyl-2-dicyanosuccinate, di-n-butyl 2,3-dicyclohexyl-2-dicyanosuccinate, diisobutyl 2,3-dicyclohexyl-2-dicyanosuccinate, 1-methyl-4-ethyl 2,3-dicyclohexyl-2-cyanosuccinate (R 1 = methyl, R 2 =ethyl), 2,3-dicyclohexyl-2-cyanosuccinic acid-1-ethyl ester-4-methyl ester (R 1 =Ethyl, R 2 = methyl), 2,3-dicyclohexyl-2-cyanosuccinic acid-1-n-butyl-4-ethyl ester (R 1 = n-butyl, R 2 =ethyl), 2,3-dicyclohexyl-2-cyanosuccinic acid-1-ethyl ester-4-n-butyl ester (R 1 =Ethyl, R 2 =n-butyl). Among them, at least one of 2,3-diisopropyl-2-dicyanosuccinate diethyl ester, 2,3-diisopropyl-2-dicyanosuccinate di-n-propyl ester, 2,3-diisopropyl-2-dicyanosuccinate diisopropyl ester, 2,3-diisopropyl-2-dicyanosuccinate di-n-butyl ester, and 2,3-diisopropyl-2-dicyanosuccinate diisobutyl ester is further preferred. The above-mentioned external electron donor compounds can be used alone or in combination.

[0044] Optionally, in the present invention, the 2,3-dinon-linear alkyl-2-cyanosuccinic acid diester compound is prepared according to the method disclosed in International Patent Application No. PCT / CN2010 / 000202.

[0045] Optionally, the molar ratio of the organoaluminum compound to the cyanate ester external electron donor is 0.5:1 to 100:1, preferably 1:1 to 50:1, based on the molar ratio of aluminum element to cyano group.

[0046] Optionally, the diol ester external electron donor compound has a structure represented by general formula (II):

[0047]

[0048] In the general formula (II), R1 to R6, R 1 ~R 2n The groups are independently selected from hydrogen, halogen, substituted or unsubstituted straight or branched C1-C 20 Alkyl, substituted or unsubstituted C3~C 20 Cycloalkyl, substituted or unsubstituted C6~C 20 Aryl, substituted or unsubstituted C7~C 20 Alkyl, substituted or unsubstituted C7~C 20 Arylalkyl, substituted or unsubstituted C2~C 10 Alkenyl, substituted or unsubstituted C 10 ~C 20 Condensed ring aromatic or substituted or unsubstituted C 10 ~C 20 Ester group.

[0049] Optionally, R1 and R2 are not hydrogen, R3 to R6 and R 1 ~R 2n Any one of the groups optionally contains one or more heteroatoms as a substitute for a carbon atom or a hydrogen atom or both, wherein the heteroatoms are selected from nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atoms, R3 to R6 and R 1 ~R 2n One or more of the groups may optionally form a ring with each other, and n is an integer of 0 to 10.

[0050] Among the compounds represented by the above general formula (II), preferably included are compounds represented by the general formula (III):

[0051]

[0052] In the general formula (III), R1 to R6, R 1 ~R 2 independently selected from hydrogen, halogen atoms, straight or branched C1-C 20 Alkyl, C3~C 20 Cycloalkyl, C6~C 20 Aryl, C7~C 20 Alkyl or C7~C 20 Aralkyl.

[0053] The above-mentioned external electron donor compound is disclosed in Chinese patents CN1436766A and CN1436796A, and all relevant contents disclosed in the patents are incorporated into the present invention as reference.

[0054] Optionally, the compound represented by the general formula (III) includes 2-ethyl-1,3-propanediol dibenzoate, 2-propyl-1,3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzoate, 1,3-butanediol dimethyl benzoate, 2-methyl-1,3-butanediol dichlorobenzoate, 2,3-dimethyl-1,3-butanediol dibenzoate, 1,3-pentanediol dimethyl benzoate, diol pivalate, 2,4-pentanediol dibenzoate, 2-methyl-1,3-pentanediol benzoic acid cinnamate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2,4-heptanediol dibenzoate, 2-methyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, etc., preferably 2,4-pentanediol dibenzoate and 4-ethyl-3,5-heptanediol dibenzoate.

[0055] Optionally, the amount of the glycol ester external electron donor added is 0.5:1 to 100:1, preferably 1:1 to 50:1, in terms of the molar ratio of the organoaluminum compound to the glycol ester external electron donor.

[0056] Optionally, the addition ratio of the three external electron donor compounds, namely, the silane external electron donor compound, the cyanate external electron donor compound and the diol ester external electron donor compound, is 1:0.01-100:0.01-100 in molar ratio, preferably 1:0.02-50:0.02-50.

[0057] The present invention also provides a method for polymerizing polyolefins, the method comprising: contacting one or more olefin monomers with the catalyst system provided by the present invention under olefin polymerization conditions, at least two of the olefin monomers are olefins represented by the general formula CH2=CHR, wherein R is hydrogen or a C1-C6 alkyl group. The method for polymerizing polyolefins provided by the present invention can be used to copolymerize two or more olefin monomers. Specific examples of the olefin monomers include, but are not limited to, at least one of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene. Preferably, the olefin monomer is at least one of ethylene, propylene, 1-n-butene, 4-methyl-1-pentene and 1-n-hexene. More preferably, the olefin monomers are propylene, ethylene and 1-n-butene.

[0058] According to the present invention, the solid catalyst component, the organic aluminum compound as a co-catalyst and the external electron donor compound can be contacted before contacting the olefin monomer, which is called "pre-contact" or "pre-complexation" in the industry; the three components can also be added to the olefin monomer separately before the polymerization reaction, that is, no "pre-contact" is implemented. According to the olefin polymerization method provided by the present invention, it is preferred that the components in the olefin polymerization catalyst system adopt the "pre-contact" method. The time of "pre-contact" is 0.1 to 60 minutes, preferably 1 to 40 minutes; the temperature of "pre-contact" is -20°C to 80°C, preferably 0°C to 60°C.

[0059] The catalyst system is first polymerized to a certain extent in the presence of a small amount of olefin monomer to obtain a prepolymerized catalyst, and then the prepolymerized catalyst is further contacted with the olefin monomer to react to obtain an olefin polymer. This technology is called the "prepolymerization" process in the industry, which helps to improve the polymerization activity of the catalyst and the bulk density of the polymer. According to the olefin polymerization method provided by the present invention, the "prepolymerization" process can be adopted, or the "prepolymerization" process can not be adopted, and the "prepolymerization" process is preferably adopted. The "prepolymerization" ratio is 1 to 1000 g polymer / g catalyst when the olefin monomers are ethylene, propylene and butene, preferably 2 to 500 g polymer / g catalyst; the temperature of the "prepolymerization" is -20°C to 80°C, preferably 0°C to 50°C.

[0060] According to the polymerization method for preparing polyolefin with high melt strength of the present invention, the polymerization conditions may be conventional conditions in the art, and the amount of catalyst used may be the amount of various catalysts used in the prior art.

[0061] The present invention also provides the above-mentioned ethylene-propylene-butylene terpolymer with wide molecular weight distribution and high melt strength, and the application of the ethylene-propylene-butylene terpolymer with wide molecular weight distribution and high melt strength obtained by the above-mentioned preparation method in the fields of pipes, plates, sheets, thermoforming and foaming. DETAILED DESCRIPTION

[0062] The present invention will be specifically described by way of examples, but the present invention is not limited to the following examples.

[0063] The test method involved in the present invention is as follows:

[0064] (1) Titanium content in catalyst: tested by 721 spectrophotometer.

[0065] (2) Melt index (MI) of polymer: measured according to the test standard GB / T3682-2000.

[0066] (3) Content of internal electron donor in catalyst component (cyanate content): measured by Waters 600E liquid chromatography.

[0067] (4) Activity: Catalyst activity = (mass of polyolefin produced) g / (mass of catalyst solid component) g.

[0068] (5) Polymer molecular weight distribution M z+1 / M n : PL-GPC220 was used with trichlorobenzene as solvent at 150°C (standard sample: polystyrene, flow rate: 1.0 ml / min, column: 3xPlgel 10um MlxED-B300x7.5nm).

[0069] (6) Melt strength: A Rheoten melt strength tester produced by Geottfert Werkstoff Pruefmaschinen of Germany was used. The instrument comprises a pair of rollers rotating in opposite directions. The polymer melt is extruded from a capillary and stretched vertically through the rollers. The stretching force can be measured by a measuring element.

[0070] Example 1

[0071] (1) Preparation of catalyst components

[0072] The catalyst components were prepared according to patent CN201510707980.3, with a titanium content of 2.8%, a 3,5-heptanediol dibenzoate (abbreviated as "S") content of 2.8%, and a 2,3-diisopropyl-2-dicyanosuccinic acid diethyl ester (abbreviated as "JS1") content of 13.7%.

[0073] (2) Olefin polymerization

[0074] Using ethylene, propylene and 1-n-butene as olefins, polymerization was carried out according to the following steps:

[0075] In a 5-liter stainless steel autoclave with a stirrer, after replacing with nitrogen, 5 ml of a hexane solution of triethylaluminum (the concentration of triethylaluminum is 0.5 mmol / m1) was introduced in a nitrogen flow at room temperature, 0.8 ml of a hexane solution of the first external electron donor 2,2-diisobutyl-1,3-dimethoxysilane (DIBMP) (the concentration of DIBMP is 0.10 mmol / ml), 10 ml of anhydrous hexane and 10 mg of a solid catalyst component were added, and pre-contacted at 8°C for 8 min; 3.5 ml of a hexane solution of the second external electron donor JS1 (the concentration of JS1 is 0.02 mmol / ml) was added, and pre-contacted at 8°C for 6 min; 3.5 ml of a hexane solution of the third external electron donor S (the concentration of 3,5-heptanediol dibenzoate is 0.02 mmol / ml) was added, and pre-contacted at 8°C for 6 min. The autoclave was closed, and 0.05 mol of hydrogen, 5 mol of propylene, 0.5 mol of ethylene and 0.3 mol of 1-n-butene were introduced. Stirring was started, and after prepolymerization at 18°C ​​for 25 minutes, 0.3 mol of hydrogen, 15 mol of propylene, 3.0 mol of ethylene and 1.7 mol of 1-n-butene were introduced, and the temperature was raised to 70°C within 10 minutes. After polymerization at 70°C for 2 hours, stirring was stopped, unpolymerized hydrogen, 1-n-butene, propylene and ethylene monomers were removed, and the polymer was collected.

[0076] Example 2

[0077] (1) Preparation of catalyst components

[0078] Same as Example 1.

[0079] (2) Olefin polymerization

[0080] The process is the same as in Example 1 except that the external electron donor 2,2-diisobutyl-1,3-dimethoxysilane (DIBMP) is replaced by cyclohexylmethyldimethoxysilane (CHMMS).

[0081] Example 3

[0082] (1) Preparation of catalyst components

[0083] Same as Example 1.

[0084] (2) Olefin polymerization

[0085] The same procedures as in Example 1 were followed except that the hexane solution of 2,2-diisobutyl-1,3-dimethoxysilane (DIBMP) was changed from 0.8 ml to 1.6 ml.

[0086] Example 4

[0087] (1) Preparation of catalyst components

[0088] Same as Example 1.

[0089] (2) Olefin polymerization

[0090] The same procedures as in Example 1 were followed except that the hexane solution of the second external electron donor was changed from 3.5 ml to 5.0 ml and the hexane solution of the third external electron donor was changed from 3.5 ml to 5.0 ml.

[0091] Example 5

[0092] (1) Preparation of catalyst components

[0093] Same as Example 1.

[0094] (2) Olefin polymerization

[0095] The same procedures as in Example 1 are followed except that the hexane solution of the second external electron donor is changed from 3.5 ml to 1.0 ml and the hexane solution of the third external electron donor is changed from 3.5 ml to 1.0 ml.

[0096] Example 6

[0097] (1) Preparation of catalyst components

[0098] Same as Example 1.

[0099] The same as Example 1 except that “introducing 0.05 mol of hydrogen, 5 mol of propylene, 0.5 mol of ethylene and 0.3 mol of 1-n-butene” and “introducing 0.3 mol of hydrogen, 15 mol of propylene, 3.0 mol of ethylene and 1.7 mol of 1-n-butene” are changed to “introducing 0.05 mol of hydrogen, 8 mol of propylene, 0.8 mol of ethylene and 0.5 mol of 1-n-butene” and “introducing 0.3 mol of hydrogen, 12 mol of propylene, 2.7 mol of ethylene and 2.8 mol of 1-n-butene”.

[0100] Example 7

[0101] (1) Preparation of catalyst components

[0102] Same as Example 1.

[0103] (2) Olefin polymerization

[0104] The same as Example 1 except that “introducing 0.05 mol of hydrogen, 5 mol of propylene, 0.5 mol of ethylene and 0.3 mol of 1-n-butene” and “introducing 0.3 mol of hydrogen, 15 mol of propylene, 3.0 mol of ethylene and 1.7 mol of 1-n-butene” are changed to “introducing 0.03 mol of hydrogen, 3 mol of propylene, 0.3 mol of ethylene and 0.2 mol of 1-n-butene” and “introducing 0.32 mol of hydrogen, 17 mol of propylene, 2.2 mol of ethylene and 3.3 mol of 1-n-butene”.

[0105] Example 8

[0106] (1) Preparation of catalyst components

[0107] Same as Example 1.

[0108] (2) Olefin polymerization

[0109] Using propylene, ethylene and 1-n-butene as olefins, polymerization was carried out according to the following steps:

[0110] Except that the prepolymerization time of 20 min was changed to 5 min, the other steps were the same as those in Example 1.

[0111] Example 9

[0112] (1) Preparation of catalyst components

[0113] Same as Example 1.

[0114] (2) Olefin polymerization

[0115] The process is the same as in Example 1 except that the first external electron donor is changed from 3,5-heptanediol dibenzoate (abbreviated as "S") to 2,4-pentanediol dibenzoate (abbreviated as "F").

[0116] Comparative Example 1

[0117] (1) Preparation of catalyst components

[0118] Take 10g of alkoxymagnesium of the same specification as in Example 1, 50ml of toluene, and 2.5ml of di-n-butyl phthalate (abbreviated as "DNBP") to prepare a suspension; add 10ml of toluene and 90ml of titanium tetrachloride to a 300ml reactor that has been repeatedly replaced with high-purity nitrogen, heat it to 80°C, then add the prepared suspension to the reactor, keep it at this temperature for 1 hour, continue to heat it to 115°C, keep it at this temperature for 2.5 hours, and then filter the liquid clean. Then add 120ml of toluene and 30ml of titanium tetrachloride to a mixed solution, heat it to 110°C, stir it for 1 hour, do this 3 times, filter out the liquid, wash the obtained solid with 150ml of hexane 4 times, filter out the liquid and dry it to obtain a solid catalyst component. The titanium content is 2.4%, and the di-n-butyl phthalate content is 13.93%.

[0119] (2) Olefin polymerization

[0120] Using propylene, ethylene and 1-n-butene as olefins, polymerization was carried out according to the following steps: In a 5-liter stainless steel autoclave with a stirrer, after replacing with nitrogen, 5 ml of a hexane solution of triethylaluminum (the concentration of triethylaluminum was 0.5 mmol / ml), 1.0 ml of a hexane solution of 2,2-diisobutyl-1,3-dimethoxysilane (DIBMP) (the concentration of DIBMP was 0.10 mmol / ml), 10 ml of anhydrous hexane and 10 mg of a solid catalyst component were introduced in a nitrogen stream at room temperature. The autoclave was closed, 0.35 mol of hydrogen, 20 mol of propylene, 3.5 mol of ethylene and 2.0 mol of 1-n-butene were introduced, stirring was started, and the temperature was raised to 70°C within 10 minutes. After polymerization reaction at 70°C for 2 hours, stirring was stopped, unpolymerized propylene monomer was removed, and the polymer was collected.

[0121] Table 1 Electron donor composition of catalyst

[0122]

[0123]

[0124] Table 2 Aggregate data

[0125]

[0126] From the data comparison in the above table, it can be seen that the terpolymer M obtained by using the catalyst system of the present invention z+1 / M n Wide molecular weight distribution, many macromolecules, and high melt strength. In the present invention, a Ziegler-Natta catalyst component containing internal electron donors such as cyanoesters and diol esters and / or other types of compounds is used. When the catalyst is composed, a unique catalyst system is formed by rationally compounding three different types of external electron donors, namely silanes, cyanoesters and diol esters. The prepared ethylene-propylene-butylene terpolymer has a wide molecular weight distribution and a high proportion of ultra-large molecules. The ultra-high molecular weight fraction ensures its high melt strength, and the wide M z+1 / M n The molecular weight distribution ensures good processing performance of the copolymer. The method provided by the invention is simple, easy to industrialize, can prepare high-performance products, and has broad application prospects.

[0127] Any numerical value mentioned in the present invention, if there is only an interval of two units between any minimum value and any maximum value, includes all values ​​from the minimum value to the maximum value each time increasing by one unit. For example, if the amount of a component, or the value of a process variable such as temperature, pressure, time, etc. is declared to be 50-90, in this specification it means that 51-89, 52-88... and 69-71 and 70-71 are specifically listed. For non-integer values, 0.1, 0.01, 0.001 or 0.0001 can be appropriately considered as a unit. These are just some specially specified examples. In this application, in a similar manner, all possible combinations of numerical values ​​between the listed minimum and maximum values ​​are considered to have been disclosed.

[0128] 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-butylene terpolymer with a wide molecular weight distribution and high melt strength, characterized in that: The molecular weight distribution M of the ethylene-propylene-butylene terpolymer z+1 / M n It is 60 to 150.

2. The ethylene-propylene-butylene terpolymer according to claim 1, characterized in that The melt strength of the ethylene-propylene-butylene terpolymer is 0.20-0.85N.

3. A method for preparing a terpolymer of ethylene, propylene and butene with a wide molecular weight distribution and high melt strength, characterized in that: Under olefin polymerization conditions, ethylene, propylene and butene are contacted with the catalyst system to react and form an ethylene-propylene-butene terpolymer; The catalyst system comprises the following components and reaction products thereof: A, a catalyst component; the catalyst component comprises titanium, a glycol ester internal electron donor compound and a cyano ester internal electron donor compound; B. Organoaluminum compounds; C. External electron donor compounds; the external electron donor compounds include silane external electron donor compounds, cyanate external electron donor compounds and glycol ester external electron donor compounds.

4. The preparation method according to claim 3, characterized in that: The catalyst component, the organoaluminum compound and the external electron donor compound are pre-contacted before contacting ethylene, propylene and butene; the pre-contact time is 0.1 to 60 minutes, preferably 1 to 40 minutes; the pre-contact temperature is -20°C to 80°C, preferably 0°C to 60°C; Preferably, the catalyst component, the organoaluminum compound and the silane external electron donor compound are first pre-contacted, then pre-contacted with the cyanate external electron donor compound, and then pre-contacted with the glycol ester external electron donor compound; And / or, the catalyst system is first prepolymerized to a certain extent in the presence of a small amount of ethylene, propylene and butene to obtain a prepolymerized catalyst, and then the prepolymerized catalyst is further contacted with ethylene, propylene and butene to react to obtain an ethylene-propylene-butene terpolymer; the prepolymerization ratio is 1 to 1000 g polymer / g catalyst, preferably 2 to 500 g polymer / g catalyst; the prepolymerization temperature is -20°C to 80°C, preferably 0°C to 50°C.

5. The preparation method according to claim 3 or 4, characterized in that: The polymerization conditions include: polymerization temperature of 0°C to 100°C, preferably 30°C to 90°C, and time of 20 to 600 min, preferably 30 to 500 min.

6. The preparation method according to any one of claims 3 to 5, characterized in that: Based on the total weight of the catalyst component, it contains 1.0 wt% to 5.0 wt% of titanium element, 0.5 wt% to 10.0 wt% of a glycol ester internal electron donor compound, and 3.0 wt% to 20.0 wt% of a cyanate internal electron donor compound, and the molar ratio of the glycol ester internal electron donor compound to the cyanate internal electron donor compound is 0.025:1 to 0.8:1; Preferably, based on the total weight of the catalyst component, it contains 1.3% to 4.0% by weight of titanium element, 0.8% to 6% by weight of diol ester internal electron donor compound, 5% to 15% by weight of cyanate internal electron donor compound, and the molar ratio of the diol ester internal electron donor compound to the cyanate internal electron donor compound is (0.05 to 0.6):

1.

7. The preparation method according to any one of claims 3 to 6, characterized in that The cyanate internal electron donor compound and the cyanate external electron donor compound independently have a structure represented by the general formula (I): In the general formula (I), R 1 and R 2 R is independently selected from a linear C1-C4 alkyl group and a branched C1-C4 alkyl group; 3 and R 4 Independently selected from C3-C6 isoalkyl, C3-C6 secondary alkyl and C3-C6 cycloalkyl; Preferably, the cyanate internal electron donor compound and the cyanate external electron donor compound are independently selected from cyanosuccinate compounds, more preferably 2,3-dinon-linear alkyl-2-cyanosuccinate diester compounds, and more preferably 2,3-diisopropyl-2-dicyanosuccinic acid dimethyl ester, 2,3-diisopropyl-2-dicyanosuccinic acid diethyl ester, 2,3-diisopropyl-2-dicyanosuccinic acid di-n-propyl ester, 2,3-diisopropyl-2-dicyanosuccinic acid di-n-propyl ester, 2,3-diisopropyl-2-dicyanosuccinic acid di-n-butyl ester, 2,3-diisopropyl-2-dicyanosuccinic acid di-isobutyl ester, 2,3-diisopropyl-2-dicyanosuccinic acid-1-methyl-4-ethyl ester, 2,3 -Diisopropyl-2-cyanosuccinic acid-1-ethyl-4-methyl ester, 2,3-diisopropyl-2-cyanosuccinic acid-1-n-butyl-4-ethyl ester, 2,3-diisopropyl-2-cyanosuccinic acid-1-ethyl-4-n-butyl ester, 2,3-diisobutyl-2-dicyanosuccinic acid-dimethyl ester, 2,3-diisobutyl-2-dicyanosuccinic acid-diethyl ester, 2, 3-Diisobutyl-2-dicyanosuccinate di-n-propyl ester, 2,3-Diisobutyl-2-dicyanosuccinate di-n-butyl ester, 2,3-Diisobutyl-2-dicyanosuccinate di-n-butyl ester, 2,3-Diisobutyl-2-dicyanosuccinate di-isobutyl ester, 2,3-Diisobutyl-2-dicyanosuccinate-1-methyl-4-ethyl ester, 2,3-Diisobutyl-2-cyanosuccinate 2,3-diisobutyl-2-cyanosuccinic acid-1-ethyl-4-methyl ester, 2,3-diisobutyl-2-cyanosuccinic acid-1-ethyl-4-butyl ester, 2,3-diisobutyl-2-cyanosuccinic acid-1-ethyl-4-butyl ester, 2,3-di-sec-butyl-2-dicyanosuccinic acid dimethyl ester, 2,3-di-sec-butyl-2-dicyanosuccinic acid diethyl ester, 2,3-di-sec-butyl-2-dicyanosuccinic acid Di-n-propyl dicyanosuccinate, diisopropyl 2,3-di-sec-butyl-2-dicyanosuccinate, di-n-butyl 2,3-di-sec-butyl-2-dicyanosuccinate, diisobutyl 2,3-di-sec-butyl-2-dicyanosuccinate, 1-methyl-4-ethyl 2,3-di-sec-butyl-2-cyanosuccinate, 1-ethyl-2,3-di-sec-butyl-2-cyanosuccinate 2,3-di-sec-butyl-2-cyanosuccinic acid-1-butyl-4-ethyl ester, 2,3-di-sec-butyl-2-cyanosuccinic acid-1-ethyl-4-butyl ester, 2,3-dicyclopentyl-2-dicyanosuccinic acid dimethyl ester, 2,3-dicyclopentyl-2-dicyanosuccinic acid diethyl ester, 2,3-dicyclopentyl-2-dicyanosuccinic acid diethyl ester, 2,3-dicyclopentyl-2-dicyanosuccinic acid dimethyl ester 2,3-dicyclopentyl-2-dicyanobutanedioic acid-1-methyl-4-ethyl ester, 2,3-dicyclopentyl-2-dicyanobutanedioic acid-1-ethyl-4-methyl ester, ...3-Dicyclopentyl-2-cyanosuccinic acid-1-butyl-4-ethyl ester, 2,3-dicyclopentyl-2-cyanosuccinic acid-1-ethyl-4-butyl ester, 2,3-dicyclohexyl-2-dicyanosuccinic acid dimethyl ester, 2,3-dicyclohexyl-2-dicyanosuccinic acid diethyl ester, 2,3-dicyclohexyl-2-dicyanosuccinic acid di-n-propyl ester, 2,3-dicyclohexyl-2-dicyanosuccinic acid diisopropyl ester, 2,3-dicyclohexyl-2-dicyanosuccinic acid dimethyl ester, 2,3-dicyclohexyl-2-dicyanosuccinic acid diethyl ester, 2,3-dicyclohexyl-2-dicyanosuccinic acid di-n-propyl ester, 2,3-dicyclohexyl-2-dicyanosuccinic acid diisopropyl ester, 2,3-dicyclohexyl-2 - at least one of di-n-butyl dicyanosuccinate, diisobutyl 2,3-dicyclohexyl-2-dicyanosuccinate, 1-methyl-4-ethyl 2,3-dicyclohexyl-2-cyanosuccinate, 1-ethyl-4-methyl 2,3-dicyclohexyl-2-cyanosuccinate, 1-n-butyl-4-ethyl 2,3-dicyclohexyl-2-cyanosuccinate, and 1-ethyl-4-n-butyl 2,3-dicyclohexyl-2-cyanosuccinate; And / or, the diol ester internal electron donor compound and the diol ester external electron donor compound independently have a structure represented by general formula (II): In the general formula (II), R1 to R6, R 1 ~R 2n The groups are independently selected from hydrogen, halogen, substituted or unsubstituted straight or branched C1-C 20 Alkyl, substituted or unsubstituted C3~C 20 Cycloalkyl, substituted or unsubstituted C6~C 20 Aryl, substituted or unsubstituted C7~C 20 Alkyl, substituted or unsubstituted C7~C 20 Arylalkyl, substituted or unsubstituted C2~C 10 Alkenyl, substituted or unsubstituted C 10 ~C 20 Condensed ring aromatic or substituted or unsubstituted C 10 ~C 20 Ester group; Preferably, in the general formula (II), R1 and R2 are not hydrogen, R3 to R6 and R 1 ~R 2n Any one of the groups optionally contains one or more heteroatoms as a substitute for a carbon atom or a hydrogen atom or both, wherein the heteroatoms are selected from nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atoms, R3 to R6 and R 1 ~R 2n One or more of the groups optionally form a ring with each other, and n is an integer from 0 to 10; Preferably, the compound represented by general formula (II) comprises a compound represented by general formula (III): In the general formula (III), R1 to R6, R 1 ~R 2 independently selected from hydrogen, halogen atoms, straight or branched C1-C 20 Alkyl, C3~C 20 Cycloalkyl, C6~C 20 Aryl, C7~C 20 Alkyl or C7~C 20 Aralkyl; Preferably, the compound represented by the general formula (III) includes at least one of 2-ethyl-1,3-propanediol dibenzoate, 2-propyl-1,3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzoate, 1,3-butanediol dimethyl benzoate, 2-methyl-1,3-butanediol di-m-chlorobenzoate, 2,3-dimethyl-1,3-butanediol dibenzoate, 1,3-pentanediol pivalate, 2,4-pentanediol dibenzoate, 2-methyl-1,3-pentanediol benzoic acid cinnamate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2,4-heptanediol dibenzoate, 2-methyl-3,5-heptanediol dibenzoate and 4-ethyl-3,5-heptanediol dibenzoate.

8. The preparation method according to any one of claims 3 to 7, characterized in that: The general formula of the organoaluminum compound is AlR n X 3-n , where R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n is an integer of 0 < n ≤ 3; Preferably, the organoaluminum compound is at least one selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, diethylaluminum monochloride, diisobutylaluminum monochloride, and ethylaluminum dichloride; And / or, the silane external electron donor compound is selected from the general formula R1R2 m Si(OR3) 3-m 、R4 n Si(OR5) 4-n and R6R7Si(OR8)2, wherein m and n are independently integers of 0 to 2; R1 and R2 are the same or different C1 to C 10 A straight chain, branched or cyclic aliphatic group; R3, R4, R5, R6 and R8 are the same or different C1-C3 straight chain aliphatic groups; R7 is a C3-C6 branched or cyclic aliphatic group; Preferably, the silane-based external electron donor compound is selected from at least one of tetramethoxysilane, n-propyltriethoxysilane, isobutyltriethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, n-propyltrimethoxysilane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisobutyldimethoxysilane, methylcyclohexyldimethoxysilane, methylisobutyldimethoxysilane, dicyclohexyldimethoxysilane, phenyltrimethoxysilane, and dicyclopentyldimethoxysilane.

9. The preparation method according to any one of claims 3 to 8, characterized in that: The ratio between the organoaluminum compound and the catalyst component is 5 to 5000, preferably 20 to 500, in terms of the molar ratio of aluminum element to titanium element; And / or, the molar ratio of the organoaluminum compound to the silane-based external electron donor compound is 0.5:1 to 200:1, preferably 1:1 to 100:1, based on the molar ratio of aluminum element to silicon element; And / or, the molar ratio of the organoaluminum compound to the cyanate ester external electron donor compound is 0.5:1 to 100:1, preferably 1:1 to 50:1, based on the molar ratio of aluminum element to cyano group; and / or, the molar ratio of the organoaluminum compound to the diol ester external electron donor compound is 0.5:1 to 100:1, preferably 1:1 to 50:1; And / or, the molar ratio of the silane-based external electron donor compound, the cyanate-based external electron donor compound and the diol ester-based external electron donor compound is 1:0.01-100:0.01-100, preferably 1:0.02-50:0.02-50.

10. Use of the ethylene-propylene-butadiene terpolymer with wide molecular weight distribution and high melt strength as claimed in claim 1 or 2, or the ethylene-propylene-butadiene terpolymer with wide molecular weight distribution and high melt strength obtained by the preparation method as claimed in any one of claims 3 to 9 in the fields of pipes, sheets, thermoforming and foaming.

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