1-butene / alpha-olefin copolymers and process for their preparation

Abstract

The application relates to the field of polybutene, and provides a long-chain branched 1-butene / alpha-olefin copolymer and a preparation method thereof. The 1-butene / alpha-olefin copolymer contains a structure of omega-olefin-based dihalosilane inserted into a main chain of the 1-butene / alpha-olefin copolymer, and the molar percentage content of Si atoms in the 1-butene / alpha-olefin copolymer is 0.0001 ‰-1 ‰. The H type long-chain branched 1-butene / alpha-olefin copolymer has high creep resistance and mechanical properties.

Description

Technical Field

[0001] This invention relates to the field of polybutene, and more specifically to a 1-butene / α-olefin copolymer containing a long-chain branched structure and its preparation method. Background Technology

[0002] Polybutene is a high-end polyolefin material with excellent mechanical properties such as creep resistance and environmental stress cracking resistance, and is widely used in hot water pipes, film packaging, medical devices, cable fibers, and other fields. However, polybutene melt crystallization usually tends to form a kinetically advantageous tetragonal type II crystal, which then transforms into the thermodynamically stable trigonal type I crystal. This complex polymorphism and crystal transformation makes it difficult to control the crystal structure, and the transformation process, which can take up to 7 days, significantly increases industrial production costs. Recent studies have shown that preparing 1-butene copolymers is an effective means of controlling the crystal structure. Copolymerization with short-chain α-olefins (including ethylene, propylene, and 1-pentene) can significantly accelerate the crystal transformation process. This is because copolymerization of 1-butene with short-chain α-olefins enhances the flexibility of the chain segments, increasing the polymer chain rearrangement ability and promoting the type II-I crystal transformation. However, the introduction of excessive short-chain α-olefins significantly lowers the crystallization and melting temperatures of the copolymer, reduces mechanical properties, and drastically reduces its creep resistance. Summary of the Invention

[0003] The purpose of this invention is to provide an H-type long-chain branched 1-butene / α-olefin copolymer and its preparation method. The H-type long-chain branched 1-butene / α-olefin copolymer of this invention has high creep resistance and mechanical properties.

[0004] To achieve the above objectives, in a first aspect, the present invention provides a 1-butene / α-olefin copolymer, wherein the 1-butene / α-olefin copolymer contains a structure in which ω-olefinic dihalosilane is inserted into the main chain of the 1-butene / α-olefin copolymer, and the molar percentage of Si atoms in the 1-butene / α-olefin copolymer is 0.0001‰-1‰.

[0005] Preferably, the 1-butene / α-olefin copolymer contains an H-type long-chain branched structure as shown in formula (I).

[0006]

[0007] In the formula, n is an integer from 0 to 10, k is an integer from 0 to 18, R is a hydrogen atom or a C1-C3 alkyl group, and R1 is a C2-C3 alkyl group. 20 α-olefinic group, R2 is C1-C 20 Straight-chain, branched, or isomerized alkyl groups, It is the backbone of a 1-butene / α-olefin copolymer.

[0008] Preferably, the ω-olefinic dihalosilane is selected from general formula R 1 SiX2R 2 At least one of the compounds with the structure shown, in the general formula, R 1 An olefinic group with 2-20 carbon atoms and a terminal olefinic double bond, R 2 X is a straight-chain, branched, or isomerized alkyl group with 1-20 carbon atoms, and X is a halogen.

[0009] Preferably, the ω-olefinic dihalosilane is 11-dodecenylmethyldichlorosilane, 11-dodecenylethyldichlorosilane, 11-dodecenylisopropyldichlorosilane, 9-decenylmethyldichlorosilane, 9-decenylethyldichlorosilane, 9-decenylbutyldichlorosilane, 8-nonenylmethyldichlorosilane, 8-nonenylethyldichlorosilane, 7-octenylmethyldichlorosilane, 7-octenylethyldichlorosilane, 7-octenyl... At least one of 1, 6-heptenylmethyldichlorosilane, 6-heptenylethyldichlorosilane, 5-hexenylmethyldichlorosilane, 5-hexenylethyldichlorosilane, 4-pentenylmethyldichlorosilane, 4-pentenylethyldichlorosilane, 3-butenylmethyldichlorosilane, 3-butenylethyldichlorosilane, 7-octenylcyclohexyldichlorosilane, 5-hexenylcyclohexyldichlorosilane, and 3-butenylcyclohexyldichlorosilane.

[0010] Preferably, the weight-average molecular weight of the 1-butene / α-olefin copolymer is 1×10⁻⁶. 3 ~2×10 7 g / mol, preferably 1×10 4 -1×10 6 g / mol.

[0011] Preferably, the molecular weight distribution of the 1-butene / α-olefin copolymer is 2-20, more preferably 2-10.

[0012] Preferably, based on the total molar number of 1-butene and α-olefin monomers, the α-olefin monomer content in the 1-butene / α-olefin copolymer is 1-20 mol%, preferably 4-10 mol%.

[0013] Preferably, the α-olefin monomer is at least one selected from ethylene, propylene, and 1-pentene.

[0014] According to a second aspect of the present invention, a method for preparing a 1-butene / α-olefin copolymer is provided, wherein the method comprises: performing a copolymerization reaction of 1-butene and α-olefin monomers in the presence of ω-olefinic dihalosilane under the action of a catalyst, and subjecting the polymer product to water treatment, drying and melt mixing, wherein the catalyst is a Ziegler-Natta catalyst or a metallocene catalyst.

[0015] Preferably, the ω-olefinic dihalosilane is selected from general formula R 1 SiX2R 2 At least one of the compounds with the structure shown, in the general formula, R 1 An olefinic group with 2-20 carbon atoms and a terminal olefinic double bond, R 2 X is a straight-chain, branched, or isomerized alkyl group with 1-20 carbon atoms, and X is a halogen.

[0016] Preferably, the ω-olefinic dihalosilane is 11-dodecenylmethyldichlorosilane, 11-dodecenylethyldichlorosilane, 11-dodecenylisopropyldichlorosilane, 9-decenylmethyldichlorosilane, 9-decenylethyldichlorosilane, 9-decenylbutyldichlorosilane, 8-nonenylmethyldichlorosilane, 8-nonenylethyldichlorosilane, 7-octenylmethyldichlorosilane, 7-octenylethyldichlorosilane, 7-octenyl... At least one of 1, 6-heptenylmethyldichlorosilane, 6-heptenylethyldichlorosilane, 5-hexenylmethyldichlorosilane, 5-hexenylethyldichlorosilane, 4-pentenylmethyldichlorosilane, 4-pentenylethyldichlorosilane, 3-butenylmethyldichlorosilane, 3-butenylethyldichlorosilane, 7-octenylcyclohexyldichlorosilane, 5-hexenylcyclohexyldichlorosilane, and 3-butenylcyclohexyldichlorosilane.

[0017] Preferably, based on the total molar number of the 1-butene and the α-olefin monomer, the content of the α-olefin monomer is 1-20 mol%, preferably 4-10 mol%.

[0018] Preferably, the α-olefin monomer is at least one selected from ethylene, propylene, and 1-pentene.

[0019] Preferably, the total amount of the ω-olefinic dihalosilane is 0.001-0.2 parts by weight relative to 100 parts by weight of the polymerization monomer.

[0020] Preferably, the Ziegler-Natta catalyst is a MgCl2 supported catalytic system, which contains MgCl2, TiCl4, alkyl aluminum, and selectively contained internal and / or external electron donors.

[0021] Preferably, the co-catalyst of the Ziegler-Natta catalyst is alkylaluminum, the internal electron donor of the Ziegler-Natta catalyst is one of aromatic carboxylic acid monoesters, aromatic carboxylic acid diesters, diethers, succinates, diol esters, etc., and the external electron donor of the Ziegler-Natta catalyst is at least one of alkoxysilane compounds.

[0022] Preferably, the molar ratio of the organoaluminum compound to the external electron donor in the Ziegler-Natta catalyst is 1:1-200:1 in terms of aluminum / silicon ratio, more preferably 10:1-50:1.

[0023] Preferably, the metallocene catalyst has a Cp m R n MX q Organometallic compounds with the structure Cp being independently substituted or unsubstituted cyclopentadienyl groups and their derivatives; M being a group 4, 5, or 6 transition metal; R being a structural bridge providing stereorigor between two Cp groups; X being a halogen or a hydrocarbon group having 1-20 carbon atoms; and m = 1-2, n = 0-1, q = 2-3, and the sum of m+q equals the oxidation state of the transition metal.

[0024] Preferably, the polymerization is carried out in the presence of a co-catalyst selected from alkylaluminoxane compounds or organoborides.

[0025] Preferably, the polymerization reaction is carried out in the presence of hydrogen.

[0026] Preferably, in the polymerization reaction, the amount of hydrogen gas used is 10 parts by weight or less relative to 100 parts by weight of the polymerization monomer.

[0027] Preferably, the conditions for the polymerization reaction include: a polymerization temperature of 0-100°C and a polymerization time of 0.05-5 hours.

[0028] Preferably, the pressure of the polymerization reaction is 0.1-10 atmospheres.

[0029] Preferably, the water treatment conditions include a temperature of 50-120°C and a time of 0.2-12 hours; more preferably, the treatment conditions include a temperature of 70-110°C and a time of 0.25-2 hours.

[0030] According to a third aspect of the present invention, a 1-butene / α-olefin copolymer prepared by the method of the present invention is provided.

[0031] Through the above technical solutions, the H-type long-chain branched 1-butene / α-olefin copolymer of the present invention exhibits high creep resistance and mechanical properties. Furthermore, the novel H-type long-chain branched 1-butene / α-olefin copolymer of the present invention possesses an H-type long-chain branched structure, which can effectively improve the polymer's melt processing properties, including higher melt strength and stronger shear thinning properties, and exhibits a faster melt crystallization rate, including a type II crystallization rate and a type II-I crystallization transition rate. Attached Figure Description

[0032] Figure 1 The H-type long-chain branched 1-butene / α-olefin copolymer of Example 1 1 H-NMR spectrum.

[0033] Figure 2 This is a comparison graph of the rheological properties of the H-type long-chain branched 1-butene / propylene copolymer of Example 1 and the 1-butene / propylene copolymer of Comparative Example 1.

[0034] Figure 3 Polarized light microscope images of the spherulite growth process of the H-type long-chain branched 1-butene / propylene copolymer of Example 1 and the 1-butene / propylene copolymer of Comparative Example 1 during isothermal crystallization at 88°C.

[0035] Figure 4 This is a comparison diagram of the crystal transformation process of the H-type long-chain branched 1-butene / propylene copolymer of Example 1 and the 1-butene / propylene copolymer of Comparative Example 1.

[0036] Figure 5 This is a comparison graph showing the crystal transformation rates of the H-type long-chain branched 1-butene / propylene copolymer of Example 1 and the 1-butene / propylene copolymer of Comparative Example 1.

[0037] Figure 6 This is a comparison graph showing the creep test results of the H-type long-chain branched 1-butene / propylene copolymer of Example 1 and the 1-butene / propylene copolymer of Comparative Example 1 at 80°C and 8 MPa stress.

[0038] Figure 7 This is a comparison graph showing the tensile mechanical properties of the H-type long-chain branched 1-butene / propylene copolymer of Example 1 and the 1-butene / propylene copolymer of Comparative Example 1. Detailed Implementation

[0039] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0040] The endpoints and any values ​​of the ranges disclosed herein 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 the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0041] According to a first aspect of the present invention, a 1-butene / α-olefin copolymer is provided, wherein the 1-butene / α-olefin copolymer contains a structure in which ω-olefinic dihalosilicon is inserted into the main chain of the 1-butene / α-olefin copolymer, and the molar percentage of Si atoms in the 1-butene / α-olefin copolymer is 0.0001‰-1‰.

[0042] According to the present invention, an H-type long-chain branched structure containing the following formula (I) is formed by inserting ω-olefinic dihalosilyl into the backbone of a 1-butene / α-olefin copolymer.

[0043]

[0044] In the formula, n is an integer from 0 to 10, k is an integer from 0 to 18, R is a hydrogen atom or a C1-C3 alkyl group, and R1 is a C2-C3 alkyl group. 20 α-olefinic group, R2 is C1-C 20 Straight-chain, branched, or isomerized alkyl groups, It is the backbone of a 1-butene / α-olefin copolymer.

[0045] Specifically, the long-chain branched structure is formed by the hydrolytic condensation of ω-olefinic dihalosilanes. This is achieved through the hydrolytic condensation of dihalosilanes on the side chains of molecular chains after water treatment, with -Si-O-Si- bridging the olefin polymer molecules. Preferably, the long-chain branched structure is an "H"-type long-chain branched structure.

[0046] According to the present invention, R is a hydrogen atom or a C1-C3 alkyl group, preferably a hydrogen atom, a methyl group or a n-propyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0047] According to the present invention, R1 is C2-C 20 α-olefinic group, R2 is C1-C 20 Straight-chain, branched, or isomerized alkyl groups.

[0048] Preferably, R1 is C4-C 20 The α-olefinic group, more preferably C4-C 15 The α-olefin group, more preferably C4-C 12 α-olefin group.

[0049] As C2-C 20Specific examples of α-olefin groups include, but are not limited to, vinyl, propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl, 1-decenyl, 1-undecenyl, 1-dodecenyl, 1-tetrenyl, 1-tetradecenyl, 1-pentadecenyl, 1-hexadecenyl, 1-heptadecenyl, 1-heptadecenyl, 1-octadecenyl, 1-nonadecenyl, and 1-eicoseneyl.

[0050] Preferably, R2 is C1-C 10 The alkyl group is a straight-chain, branched, or isomerized alkyl group, more preferably a C1-C6 straight-chain, branched, or isomerized alkyl group; even more preferably a C1-C3 straight-chain, branched, or isomerized alkyl group, and particularly preferably a C1-C2 alkyl group.

[0051] As C1-C 20 Specific examples of straight-chain, branched, or isomerized alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, cyclohexyl, etc.

[0052] For example, n can be represented as: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10.

[0053] For example, k can be represented as: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18.

[0054] According to the present invention, preferably, the weight-average molecular weight of the 1-butene / α-olefin copolymer is 1×10⁻⁶. 3 -2×10 7 More preferably, the weight-average molecular weight of the 1-butene / α-olefin copolymer is 1 × 10 g / mol. 4 -1×10 6 g / mol;

[0055] According to the present invention, preferably, the molecular weight distribution of the 1-butene / α-olefin copolymer is 2-20, more preferably, the molecular weight distribution of the 1-butene / α-olefin copolymer is 2-10;

[0056] According to the present invention, preferably, the 1-butene average sequence length of the 1-butene in the 1-butene / α-olefin copolymer is 5-200, and the α-olefin average sequence length is 1.1-4. Here, the average sequence length refers to the average length of the continuous arrangement of different monomer units on the molecular chain.

[0057] According to the present invention, preferably, the ω-olefinic dihalosilane is selected from general formula R 1 SiX2R 2 At least one of the compounds with the structure shown, in the general formula, R 1 For C2-C20 α-olefinic group, X is a halogen, R 2 For C1-C 20 Straight-chain, branched, or isomerized alkyl groups.

[0058] Preferably, R 1 C4-C 20 The α-olefinic group, more preferably C4-C 15 The α-olefin group, more preferably C4-C 12 α-olefin group.

[0059] As C2-C 20 Specific examples of α-olefin groups include, but are not limited to, vinyl, propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl, 1-decenyl, 1-undecenyl, 1-dodecenyl, 1-tetrenyl, 1-tetradecenyl, 1-pentadecenyl, 1-hexadecenyl, 1-heptadecenyl, 1-heptadecenyl, 1-octadecenyl, 1-nonadecenyl, and 1-eicoseneyl.

[0060] Preferably, X is a halogen. Multiple Xs in the same general formula can be the same or different, and each can be an independent halogen (including fluorine, chlorine, bromine, and iodine); more preferably, X is chlorine.

[0061] Preferably, R 2 For C1-C 10 The alkyl group is a straight-chain, branched, or isomerized alkyl group, more preferably a C1-C6 straight-chain, branched, or isomerized alkyl group; even more preferably a C1-C3 straight-chain, branched, or isomerized alkyl group, and particularly preferably a C1-C2 alkyl group.

[0062] As C1-C 20 Specific examples of straight-chain, branched, or isomerized alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, cyclohexyl, etc.

[0063] According to the present invention, specific examples of the ω-olefinic dihalosilane include, but are not limited to: 11-dodecenylmethyldichlorosilane, 11-dodecenylethyldichlorosilane, 11-dodecenylisopropyldichlorosilane, 9-decenylmethyldichlorosilane, 9-decenylethyldichlorosilane, 9-decenylbutyldichlorosilane, 8-nonenylmethyldichlorosilane, 8-nonenylethyldichlorosilane, 7-octenylmethyldichlorosilane, and 7-octenylethyldichlorosilane. At least one of the following: alkyl, 7-octenyloctyldichlorosilane, 6-heptenylmethyldichlorosilane, 6-heptenylethyldichlorosilane, 5-hexenylmethyldichlorosilane, 5-hexenylethyldichlorosilane, 4-pentenylmethyldichlorosilane, 4-pentenylethyldichlorosilane, 3-butenylmethyldichlorosilane, 3-butenylethyldichlorosilane, 7-octenylcyclohexyldichlorosilane, 5-hexenylcyclohexyldichlorosilane, and 3-butenylcyclohexyldichlorosilane.

[0064] According to the present invention, preferably, the α-olefin monomer is at least one selected from ethylene, propylene, and 1-pentene.

[0065] According to the present invention, the molar percentage of Si atoms in the 1-butene / α-olefin copolymer is 0.0001‰-1‰, for example, 0.0001‰, 0.0003‰, 0.0005‰, 0.0008‰, 0.001‰, 0.003‰, 0.005‰, 0.008‰, 0.01‰, 0.03‰, 0.05‰, 0.08‰, 0.1‰, 0.3‰, 0.5‰, 0.8‰, 1‰, etc., as well as any two of the above ranges.

[0066] According to a second aspect of the present invention, a method for preparing a 1-butene / α-olefin copolymer is provided, wherein the method comprises: performing a copolymerization reaction of 1-butene and α-olefin monomers in the presence of ω-olefinic dihalosilane under the action of a catalyst, and subjecting the polymer product to water treatment, drying and melt mixing, wherein the catalyst is a Ziegler-Natta catalyst or a metallocene catalyst.

[0067] According to the present invention, preferably, the ω-olefinic dihalosilane is selected from general formula R 1 SiX2R 2 At least one of the compounds with the structure shown, in the general formula, R 1 For C2-C 20 α-olefinic group, X is a halogen, R 2 For C1-C 20 Straight-chain, branched, or isomerized alkyl groups.

[0068] Preferably, R 1 C4-C 20The α-olefinic group, more preferably C4-C 15 The α-olefin group, more preferably C4-C 12 α-olefin group.

[0069] As C2-C 20 Specific examples of α-olefin groups include, but are not limited to, vinyl, propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl, 1-decenyl, 1-undecenyl, 1-dodecenyl, 1-tetrenyl, 1-tetradecenyl, 1-pentadecenyl, 1-hexadecenyl, 1-heptadecenyl, 1-heptadecenyl, 1-octadecenyl, 1-nonadecenyl, and 1-eicoseneyl.

[0070] Preferably, X is a halogen. Multiple Xs in the same general formula can be the same or different, and each can be an independent halogen (including fluorine, chlorine, bromine, and iodine); more preferably, X is chlorine.

[0071] Preferably, R 2 For C1-C 10 The alkyl group is a straight-chain, branched, or isomerized alkyl group, more preferably a C1-C6 straight-chain, branched, or isomerized alkyl group; even more preferably a C1-C3 straight-chain, branched, or isomerized alkyl group, and particularly preferably a C1-C2 alkyl group.

[0072] As C1-C 20 Specific examples of straight-chain, branched, or isomerized alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, cyclohexyl, etc.

[0073] According to the present invention, specific examples of the ω-olefinic dihalosilane include, but are not limited to: 11-dodecenylmethyldichlorosilane, 11-dodecenylethyldichlorosilane, 11-dodecenylisopropyldichlorosilane, 9-decenylmethyldichlorosilane, 9-decenylethyldichlorosilane, 9-decenylbutyldichlorosilane, 8-nonenylmethyldichlorosilane, 8-nonenylethyldichlorosilane, 7-octenylmethyldichlorosilane, and 7-octenylethyldichlorosilane. At least one of the following: alkyl, 7-octenyloctyldichlorosilane, 6-heptenylmethyldichlorosilane, 6-heptenylethyldichlorosilane, 5-hexenylmethyldichlorosilane, 5-hexenylethyldichlorosilane, 4-pentenylmethyldichlorosilane, 4-pentenylethyldichlorosilane, 3-butenylmethyldichlorosilane, 3-butenylethyldichlorosilane, 7-octenylcyclohexyldichlorosilane, 5-hexenylcyclohexyldichlorosilane, and 3-butenylcyclohexyldichlorosilane.

[0074] According to the present invention, preferably, the total amount of the organosilane is 0.0001-10 parts by weight relative to 100 parts by weight of the total amount of polymerization monomers, more preferably 0.001-0.1 parts by weight, even more preferably 0.003-0.06 parts by weight, even more preferably 0.004-0.03 parts by weight, and particularly preferably 0.01-0.02 parts by weight. By using the organosilane within the above range, the II-I crystal form transformation rate in the obtained H-type long-chain branched 1-butene / α-olefin copolymer can be further improved.

[0075] Specific examples of the total amount of the organosilane relative to 100 parts by weight of the polymerization monomers include, for example, 0.0001 parts by weight, 0.0003 parts by weight, 0.0005 parts by weight, 0.0008 parts by weight, 0.001 parts by weight, 0.003 parts by weight, 0.005 parts by weight, 0.008 parts by weight, 0.01 parts by weight, 0.03 parts by weight, 0.05 parts by weight, 0.08 parts by weight, 0.1 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 part by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, etc., as well as any two of the above ranges.

[0076] According to the present invention, preferably, the α-olefin monomer is at least one selected from ethylene, propylene, and 1-pentene.

[0077] According to the present invention, the Ziegler-Natta catalyst used in the polymerization process is preferably a MgCl2 supported catalytic system, wherein the MgCl2 supported catalytic system contains MgCl2, TiCl4, alkyl aluminum, and selectively contained internal and / or external electron donors.

[0078] Preferably, relative to 100 parts by weight of the total solid portion of the catalyst, the Mg content is 15-25 parts by weight and the Ti content is 1.5-4.5 parts by weight.

[0079] Preferably, the co-catalyst of the Ziegler-Natta catalyst is alkylaluminum; more preferably, the co-catalyst of the Ziegler-Natta catalyst is triisobutylaluminum.

[0080] Furthermore, the internal electron donor in the Ziegler-Natta catalyst is one of aromatic carboxylic acid monoesters, aromatic carboxylic acid diesters, diethers, succinates, diol esters, etc. More preferably, the internal electron donor in the Ziegler-Natta catalyst is diisobutyl phthalate and / or 9,9-di(methoxymethyl)fluorene. Most preferably, the internal electron donor in the Ziegler-Natta catalyst is diisobutyl phthalate. The external electron donor in the Ziegler-Natta catalyst is at least one of alkoxysilane compounds. More preferably, the external electron donor in the Ziegler-Natta catalyst is diisopropyldimethoxysilane.

[0081] The metallocene catalyst typically refers to one with Cp m R n MX q Organometallic compounds with a structure in which Cp is independently a substituted or unsubstituted cyclopentadienyl group and its derivatives (such as indenyl and fluorenyl), wherein the substituents on the Cp derivatives are independently selected from hydrogen, C1-C 10 Alkyl groups and 5-7 membered cycloalkyl groups, the cycloalkyl group itself may also contain a C1-C6 alkyl group, C6-C 15 The aryl or aralkyl group is used as a substituent, wherein the two adjacent groups can further form an unsaturated ring of 4-15 carbon atoms, or Si(R)3, where R is C1-C2. 10 Alkyl, C6-C 15 aryl or C3-C 10 The metallocene is a cycloalkyl group, such as Ph, Bz, Naph, BzInd, Me, Et, n-Pr, iso-Pr, n-Bu, and tertiary-Bu, but not limited to these structures; M is a group 4, 5, or 6 transition metal, such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten; R is a structural bridge providing stereorigor between two Cp atoms; X is a halogen or a hydrocarbon group having 1-20 carbon atoms; and m = 1-2, n = 0-1, q = 2-3, the sum of m+q equals the oxidation state of the transition metal. Methods for preparing and using metallocenes are well known in the art.

[0082]

[0083] Where M is a metal from Groups 4, 5, and 6 of the periodic table, such as titanium, zirconium, hafnium, vanadium, chromium, molybdenum, and tungsten, with titanium, zirconium, and hafnium being preferred; R1 and R2 are each independently a halogen atom (fluorine, chlorine, bromine, iodine), hydrogen, or C1-C. 10 Alkyl group, C6-C 15 aryl or -OR 18 R 18 It is C1-C 10 Alkyl group, C6-C15 In the aryl, alkylaryl, arylalkyl, haloalkyl, or haloaryl groups, the alkyl group contains 1-10 carbon atoms, and the aryl group contains 6-20 carbon atoms; R3 to R6 are each an independent hydrogen atom, and the halogen atom (fluorine, chlorine, bromine, iodine) is a C1-C atom that can be halogenated. 10 Alkyl groups can be halogenated C6-C 15 Aryl, C2-C 10 alkenyl groups, C7-C 40 Aryl groups, C7-C 40 alkylaryl, C8-C 40 aryl alkenyl, -NR 19 -SR 19 -OR 19 -OSiR 19 or -PR2 19 Group (where R) 19 Halogen atoms, C1-C 10 Alkyl group, C6-C 15 (Aryl) and two adjacent groups can combine to form a ring system; R 7 for =BR 11 =AlR 11 , -Ge-, -Sn-, -O-, -S-, =SO, =SO2, =NR 11 =CO, =PR 11 or = P(O)R 11 , where R 11 R 12 and R 13 Each atom is independently a hydrogen atom, a halogen atom, and a C1-C atom. 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C6-C 30 aryl, C6-C 20 Halogenated aryl, C1-C 10 alkoxy group, C2-C 20 alkenyl groups, C7-C 40 Aryl groups, C8-C 40 aryl alkenyl group, C7-C 40 alkylaryl, or R 11 and R 12 or R 11 and R 13 It can form a substitution system together with the atoms bonded to it; Q is silicon, germanium, or tin; R 8 and R 9 Each independently possesses the ability to interact with R. 11 The meaning of the above; m and n are the same or different and are 0, 1 or 2; group R 10Each is independent and has its own R 11 R 12 and R 13 The meaning described. Two adjacent R 10 Groups can combine to form ring systems.

[0084] Examples of metallocene catalysts include: ethylbis(1-indenyl)titanium dichloride, ethylbis(1-indenyl)zirconia dichloride, dimethylsilylbis(1-indenyl)zirconia dichloride, dimethylsilylbis(2,5-dimethyl-4-(2-methylphenyl)-1-indenyl)zirconia dichloride, dimethylsilylbis(1-indenyl)hafnium dichloride, dimethylsilylbis(2-methyl-4-phenyl-1-indenyl)zirconia dichloride, dimethylsilylbis(2-methyl-4-phenyl-1-indenyl)hafnium dichloride, and dimethylsilylbis(2-methyl-4,5-benzoindenyl)titanium dichloride. Dimethylsilylbis(2-methyl-4,5-benzoindyl)zirconium chloride, dimethylsilylbis(2-methyl-4,6-diisopropylindyl)zirconium chloride, dimethylsilylbis(2-ethyl-4-phenyl-1-indyl)hafnium chloride, dimethylsilylbis(2-ethyl-4-naphthyl-1-indyl)zirconium chloride, dimethylsilylbis(2,5-dimethyl-4-(2,5-dimethylphenyl)-1-thienocyclopentadienyl)zirconium chloride, dimethylsilylbis(2,5-dimethyl-4-(2-methylphenyl)-1-thienocyclopentadienyl)zirconium chloride.

[0085] Preferably, the metallocene cocatalyst is selected from alkylaluminoxane compounds or organoborides. The alkylaluminoxanes are preferably methylaluminoxanes, modified methylaluminoxanes (including modified methylaluminoxanes obtained by partially substituting methyl groups with ethyl and / or isobutyl groups; modified methylaluminoxanes prepared from boron compounds, silyl ethers, and polar organic compounds containing P, N, S, or O), ethylaluminoxanes, isobutylaluminoxanes, tert-butylaluminoxanes, etc. The organoborides are selected from B(C6F5)3, [Ph3C], etc. + [B(C6F5)4] - and [PhNH(Me)2] + [B(C6F5)4] - At least one of them.

[0086] According to the present invention, for alkylaluminoxane compounds, the amount of the co-catalyst added, based on the molar ratio of Al to the transition metal M in the main catalyst, is Al:M = 10-50000:1, preferably 100-5000:1; for organoborides, the amount of the co-catalyst added, based on the molar ratio of B to the transition metal M in the main catalyst, is B:M = 0.1-100:1, preferably 0.5-10:1.

[0087] According to the method of the present invention, the preparation of the metallocene catalyst used in the polymerization process is based on the following references: US5149819, US5243001, US5239022, US5296434, US5276208, CN1309669A; Zhu Hongping, et al. Chin. J. Org. Chem. 2018, 38, 2937; Luigi Resconi, et al. Chem. Rev. 2000, 100, 1253; Albert Rossi, et al. Macromolecules, 1995, 28, 1739; Huang Qigu, et al. Polym. Int. 2001, 50, 45; Luigi Resconi, et al. Macromol. Chem. Phys. 2006, 207, 2257; Ma Zhe, et al. al.Chin.J.Polym.Sci.2022,41,414; Li Yuesheng, et al.Macromolecules, 2020,53,2088; John A.Ewen, et al.J.Am.Chem.Soc.2001,123,4763.

[0088] According to the present invention, preferably, the polymerization conditions include: polymerization temperature of 0-100℃, polymerization time of 0.05-5 hours, and polymerization pressure of 0.01-1 MPa; more preferably, the polymerization conditions include: polymerization temperature of 10-80℃, polymerization time of 0.1-4 hours, and polymerization pressure of 0.01-0.4 MPa.

[0089] Furthermore, in order to adjust the molecular weight of the 1-butene / α-olefin copolymer and improve its processability, the polymerization reaction is preferably carried out in the presence of hydrogen. Preferably, the amount of hydrogen used is less than 10 parts by weight relative to 100 parts by weight of butene-1 monomer, more preferably 0.05-0.2 parts by weight.

[0090] According to the present invention, butene-1 is polymerized with ω-olefinic dihalosilane, and then the polymer undergoes hydrolytic condensation via Si-Cl bonds. In the present invention, the polymer undergoes hydrolytic condensation via Si-Cl bonds by water treatment, drying, and melt mixing of the polymer product. The water can be used in liquid or steam form. Furthermore, the amount of water used is excessive, as long as it is sufficient to allow the polymer to undergo sufficient hydrolytic condensation via Si-Cl bonds.

[0091] According to the present invention, in order to enable the polymer to undergo sufficient hydrolysis and condensation through Si-Cl bonds, preferably, the water treatment conditions include: a temperature of 50-120°C and a time of 0.2-12 hours; more preferably, the treatment conditions include: a temperature of 70-110°C and a time of 0.25-2 hours.

[0092] According to a third aspect of the present invention, a 1-butene / α-olefin copolymer prepared by the method of the present invention is provided.

[0093] The novel long-chain branched 1-butene / α-olefin copolymer resin of the present invention has an H-type long-chain branched structure, which can effectively improve the melt processing performance of the polymer, including higher melt strength and stronger shear thinning properties, including type II crystallization rate and II-I crystallization transition rate, and has higher creep resistance and mechanical properties.

[0094] The present invention will be described in detail below through embodiments, but the present invention is not limited to the following embodiments.

[0095] In the following examples and comparative examples, the gel content of the H-type long-chain branched 1-butene / α-olefin copolymer was determined according to the following method:

[0096] The 1-butene / α-olefin copolymer was dried to constant weight in a vacuum drying oven at 50°C, and the weight was recorded as W1. The dried polyolefin resin was then dissolved in xylene, and the solution was thoroughly dissolved by shaking at 135°C. The solution was filtered through a 200-mesh stainless steel mesh, and the undissolved polymer remaining on the mesh was collected. This undissolved polymer was then dried in a vacuum drying oven at 100°C for 4 hours, and the weight was recorded as W2. The formula for calculating the gel content of the 1-butene / α-olefin copolymer is as follows:

[0097] Gel content (wt%) = (W2 / W1) × 100 (wt%).

[0098] The melting temperature of the prepared 1-butene / α-olefin copolymer was measured using a differential scanning calorimeter (DSC) model Q2000 from TA Instruments.

[0099] The storage modulus of the prepared 1-butene / α-olefin copolymer at a shear frequency of 0.01 rad / s was tested using a parallel plate rheometer from TA Instruments (USA) AR2000.

[0100] The weight-average molecular weight of the prepared 1-butene / α-olefin copolymer was determined using a PL-220 high-temperature gel permeation chromatograph from Agilent Technologies, Inc.

[0101] The branched structure content of the prepared 1-butene / α-olefin copolymer was determined by high-temperature 1H NMR spectroscopy using a Bruker AVANCE III 500WB nuclear magnetic resonance spectrometer. The molar percentage of Si atoms in the 1-butene / α-olefin copolymer resin (hereinafter referred to as Si content) was calculated by the ratio of the peak area of ​​the signal peak appearing at a chemical shift of 0.23 ppm to the peak areas of the four signal peaks appearing at chemical shifts of 0.75–1.6 ppm.

[0102] The α-olefin insertion rate of the prepared 1-butene / α-olefin copolymer was determined by high-temperature carbon spectroscopy using a Bruker AVANCEIII 500WB nuclear magnetic resonance spectrometer.

[0103] The II-I crystal transformation process of the prepared 1-butene / α-olefin copolymer was monitored using a Rigaku D / max 2500 wide-angle X-ray diffractometer from Japan. The laser source was Cu Kα, the wavelength was 0.154 nm, the scanning speed was 2° / min, and the scanning range was 5° to 30°.

[0104] The creep resistance of the prepared 1-butene / α-olefin copolymer was tested using TA's DMA800, employing a three-point bending mode at 80°C and a stress of 8 MPa.

[0105] The tensile mechanical properties of the prepared 1-butene / α-olefin copolymer were tested using a universal tensile testing machine from Instron Corporation, USA.

[0106] When the internal electron donor in the Ziegler-Natta catalyst is 9,9-di(methoxymethyl)fluorene, based on the total weight of the catalyst, the composition of the catalyst contains 3.44 wt% Ti, 12.12 wt% 9,9-di(methoxymethyl)fluorene, and 18.75 wt% magnesium, hereinafter referred to as a diether-type catalyst. The specific preparation method is as follows: Weigh 5g of anhydrous MgCl2 and add it to a two-necked flask filled with argon and equipped with a magnetic stirrer. Then add 23.8mL of isooctanol and 30mL of decane. While stirring, slowly heat to 130℃ and react at 130℃ for 1h until the solution is clear. After cooling to 60-80℃, add 1.05g of phthalic anhydride and stir overnight until the solution is clear. Under an argon atmosphere, add 250mL of TiCl4 to a thoroughly dried Schlenk reactor, cool to -20℃, and slowly add the above clear solution while stirring. React at a constant temperature for 1h. The temperature was then slowly increased to 60°C, and 2.65 g of BMMF (BMMF / Mg = 0.21 mol / mol) was added. The temperature was then increased to 110°C and the reaction was carried out for 2 hours. The liquid in the reaction flask was removed by filtration, and then 250 ml of TiCl4 was added. The mixture was stirred at 110°C for 2 hours, and the liquid was removed by filtration. The mixture was washed five times with hexane at 60°C and once with hexane at room temperature. The product was then dried under vacuum to obtain a diether-type catalyst.

[0107] When the internal electron donor in the Ziegler-Natta catalyst is diisobutyl phthalate (DIBP), based on the total weight of the catalyst, the composition of the catalyst contains 2.3% by weight of Ti, 6.91% by weight of DIBP, and 21.21% by weight of magnesium, hereinafter referred to as a diester-type catalyst. The specific preparation method is as follows: Under an argon atmosphere, 150 mL of TiCl4 is added to a thoroughly dried Schlenk reactor, the temperature is lowered to -20°C, and 10.0 g of MgCl2·2.8C2H5OH support is added with stirring. The reaction is maintained at this temperature for 1 h. Then, the temperature is slowly raised to 110°C, and 3.0 mL of DIBP (DIBP / Mg = 0.25 mol / mol) is added, and the reaction is continued for 2 h. The liquid in the reaction flask is filtered out, and then 150 mL of TiCl4 is added again. The reaction is stirred at 110°C for 2 h, and the liquid is filtered out again. The catalyst was washed five times with hexane at 60°C, washed once with hexane at room temperature, and dried under vacuum to obtain a diester-type catalyst.

[0108] When the internal electron donor in the Ziegler-Natta catalyst is a mixture of 9,9-di(methoxymethyl)fluorene and diisobutyl phthalate, based on the total weight of the catalyst, the composition of the catalyst contains 2.52% by weight of Ti, 1.86% by weight of diisobutyl phthalate, 5.33% by weight of 9,9-di(methoxymethyl)fluorene, and 20.91% by weight of magnesium (hereinafter referred to as a composite catalyst). The specific preparation method is as follows: Under an argon atmosphere, 150 ml of TiCl4 is added to a thoroughly dried Schlenk reactor, the temperature is lowered to -20°C, and 10.0 g of MgCl2·2.8C2H5OH support is added with stirring. The reaction is carried out at a constant temperature for 1 h. The temperature was then slowly raised to 110°C, and a mixture of 0.8 mL of diisobutyl phthalate (DIBP) (DIBP / Mg = 0.067 mol / mol) and 1.16 g of BMMF (BMMF / Mg = 0.09 mol / mol) was added. The reaction was allowed to proceed for 2 h. The liquid in the reaction flask was removed by filtration, and then 150 mL of TiCl4 was added. The mixture was stirred at 110°C for 2 h, and the liquid was removed by filtration. The catalyst was washed five times with hexane at 60°C and once with hexane at room temperature, and then dried under vacuum to obtain the composite catalyst.

[0109] Example 1

[0110] Under vacuum, butene-1 gas was introduced into the reactor to atmospheric pressure. Then, at 50°C, 0.01 MPa of hydrogen, 0.0029 mol of triethylaluminum, 0.0024 g of 5-hexenylmethyldichlorosilane, and 30 mg of diester catalyst were added sequentially. Propylene was then rapidly added at 0.08 MPa, and the reactor was introduced into the reactor to 0.1 MPa. The reaction was then carried out for 10 min. The remaining butene-1 and propylene monomers in the reactor were then vented. After the reaction was complete, the reactor was treated with excess deionized water at 100°C for 20 min. Finally, the reactor was vacuum dried at 70°C and melt-blended to obtain 10.2 g of long-chain branched 1-butene / propylene copolymer.

[0111] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and propylene content of the 1-butene / α-olefin copolymer prepared above were tested, and the test results are shown in Table 1.

[0112] Comparative Example 1

[0113] The method of Example 1 was followed, except that no organosilane was added during the copolymerization of 1-butene and propylene, and 11.3g of 1-butene / propylene copolymer was finally obtained.

[0114] The melting temperature, storage modulus, gel content, weight-average molecular weight, and propylene content of the 1-butene / propylene copolymer prepared above were tested, and the test results are shown in Table 3.

[0115] Figure 1 The H-type long-chain branched 1-butene / propylene copolymer of Example 1 1 H-NMR spectrum; Figure 2 This is a comparison graph of the rheological properties of the H-type long-chain branched 1-butene / propylene copolymer of Example 1 and the 1-butene / propylene copolymer of Comparative Example 1. Figure 1 The peak with a chemical shift of 0.23 ppm confirms the insertion of 5-hexenylmethyldichlorosilane into the backbone of the 1-butene / propylene copolymer; Figure 2 In the rheological results, the energy storage modulus of Example 1 in the low-frequency terminal region is significantly higher than that of Comparative Example 1, exhibiting a significant long-chain branching effect. Figure 1 In 1 H-NMR spectrum and Figure 2 The rheological results show that H-type long-chain branched 1-butene / propylene copolymer was prepared in this embodiment.

[0116] Example 2

[0117] Under vacuum, butene-1 gas was introduced into the reactor to atmospheric pressure. Then, at 50°C, 0.01 MPa of hydrogen, 0.0029 mol of triethylaluminum, 0.0024 g of 7-octenylmethyldichlorosilane, and 30 mg of diester catalyst were added sequentially. Propylene was then rapidly added at 0.08 MPa, and the reactor was introduced into the reactor to 0.1 MPa with butene-1 gas. The reaction was then carried out for 10 min. The remaining butene-1 and propylene in the reactor were then vented. After the reaction was complete, the reactor was treated with deionized water at 100°C for 20 min. Finally, the reactor was vacuum dried at 70°C and melt-blended to obtain 10.1 g of long-chain branched 1-butene / propylene copolymer.

[0118] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and propylene content of the 1-butene / propylene copolymer prepared above were tested, and the test results are shown in Table 1.

[0119] The branched 1-butene / propylene copolymer was determined using the same method as in Example 1. 1 H-NMR spectrum, 13 C-NMR spectra, rheological properties, creep tests, and tensile mechanical tests showed that an H-type long-chain branched 1-butene / propylene copolymer was prepared, with good melt processing properties and significantly enhanced mechanical properties and creep resistance.

[0120] Example 3

[0121] The method of Example 1 was followed, except that the catalyst added during the polymerization reaction was a diether-type catalyst in the same amount, and 11.4g of long-chain branched 1-butene / propylene copolymer was finally obtained.

[0122] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and propylene content of the 1-butene / α-olefin copolymer prepared above were tested, and the test results are shown in Table 1.

[0123] The branched 1-butene / propylene copolymer was determined using the same method as in Example 1. 1 H-NMR spectrum, 13 C-NMR spectra, rheological properties, creep tests, and tensile mechanical tests showed that an H-type long-chain branched 1-butene / propylene copolymer was prepared, with good melt processing properties and significantly enhanced mechanical properties and creep resistance.

[0124] Comparative Example 2

[0125] The method of Example 3 was followed, except that no organosilane was added during the 1-butene / propylene copolymerization process, and 10.7g of 1-butene / propylene copolymer was finally obtained.

[0126] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and propylene content of the 1-butene / propylene copolymer prepared above were tested, and the test results are shown in Table 3.

[0127] Example 4

[0128] The method of Example 2 was followed, except that the catalyst added during the polymerization reaction was a diether-type catalyst in the same amount, and 11.8g of long-chain branched 1-butene / α-olefin copolymer was finally obtained.

[0129] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and propylene content of the 1-butene / propylene copolymer prepared above were tested, and the test results are shown in Table 1.

[0130] The branched 1-butene / propylene copolymer was determined using the same method as in Example 1. 1 H-NMR spectrum, 13 C-NMR spectra, rheological properties, creep tests, and tensile mechanical tests showed that an H-type long-chain branched 1-butene / propylene copolymer was prepared, with good melt processing properties and significantly enhanced mechanical properties and creep resistance.

[0131] Example 5

[0132] Under vacuum, butene-1 gas was introduced into the reactor to atmospheric pressure. Then, at 50°C, 0.01 MPa of hydrogen, 0.0029 mol of triethylaluminum, 0.0024 g of 5-hexenylmethyldichlorosilane, and 30 mg of diester-type catalyst were added sequentially. Ethylene was then rapidly added at 0.06 MPa, and the butene-1 gas was introduced into the reactor to 0.1 MPa. The reaction was then carried out for 10 min. The remaining butene-1 and ethylene monomers in the reactor were then vented. After the reaction was complete, the reactor was treated with excess deionized water at 100°C for 20 min. Finally, the mixture was vacuum dried at 70°C and melt-blended to obtain 10.6 g of long-chain branched 1-butene / ethylene copolymer.

[0133] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and ethylene content of the 1-butene / ethylene copolymer prepared above were tested, and the test results are shown in Table 1.

[0134] The branched 1-butene / ethylene copolymer was determined using the same method as in Example 1. 1 H-NMR spectrum, 13 C-NMR spectra, rheological properties, creep tests, and tensile mechanical tests showed that an H-type long-chain branched 1-butene / ethylene copolymer was prepared, with good melt processing properties and significantly enhanced mechanical properties and creep resistance.

[0135] Comparative Example 3

[0136] The method of Example 5 was followed, except that no organosilane was added during the 1-butene / ethylene copolymerization process, and 10.0g of 1-butene / ethylene copolymer was finally obtained.

[0137] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and ethylene content of the 1-butene / ethylene copolymer prepared above were tested, and the test results are shown in Table 3.

[0138] Example 6

[0139] Under vacuum, butene-1 gas was introduced into the reactor to atmospheric pressure. Then, at 50°C, 0.01 MPa of hydrogen, 0.0029 mol of triethylaluminum, 0.0024 g of 7-octenylmethyldichlorosilane, and 30 mg of diester catalyst were added sequentially. Ethylene was then rapidly added at 0.06 MPa, and the butene-1 gas was introduced into the reactor to 0.1 MPa. The reaction was then carried out for 10 min. The remaining butene-1 and ethylene monomers in the reactor were then vented. After the reaction was complete, the reactor was treated with excess deionized water at 100°C for 20 min. Finally, the mixture was vacuum dried at 70°C and melt-blended to obtain 11.2 g of long-chain branched 1-butene / ethylene copolymer.

[0140] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and ethylene content of the 1-butene / ethylene copolymer prepared above were tested, and the test results are shown in Table 1.

[0141] The branched 1-butene / ethylene copolymer was determined using the same method as in Example 1. 1 H-NMR spectrum, 13 C-NMR spectra, rheological properties, creep tests, and tensile mechanical tests showed that an H-type long-chain branched 1-butene / ethylene copolymer was prepared, with good melt processing properties and significantly enhanced mechanical properties and creep resistance.

[0142] Example 7

[0143] Following the method of Example 5, except that the catalyst added during the polymerization reaction was the same amount of diether catalyst, and finally 12.1g of long-chain branched 1-butene / ethylene copolymer was obtained.

[0144] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and ethylene content of the 1-butene / ethylene copolymer prepared above were tested, and the test results are shown in Table 1.

[0145] The branched 1-butene / ethylene copolymer was determined using the same method as in Example 1. 1 H-NMR spectrum, 13 C-NMR spectra, rheological properties, creep tests, and tensile mechanical tests showed that an H-type long-chain branched 1-butene / ethylene copolymer was prepared, with good melt processing properties and significantly enhanced mechanical properties and creep resistance.

[0146] Comparative Example 4

[0147] The method of Example 7 was followed, except that no organosilane was added during the 1-butene / ethylene copolymerization process, and 11.9g of 1-butene / ethylene copolymer was finally obtained.

[0148] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and ethylene content of the 1-butene / ethylene copolymer prepared above were tested, and the test results are shown in Table 3.

[0149] Example 8

[0150] The method of Example 6 was followed, except that the catalyst added during the polymerization reaction was the same amount of diether catalyst, and 12.3g of long-chain branched 1-butene / ethylene copolymer was finally obtained.

[0151] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and ethylene content of the 1-butene / ethylene copolymer prepared above were tested, and the test results are shown in Table 1.

[0152] The branched 1-butene / ethylene copolymer was determined using the same method as in Example 1. 1 H-NMR spectrum, 13 C-NMR spectra, rheological properties, creep tests, and tensile mechanical tests showed that an H-type long-chain branched 1-butene / ethylene copolymer was prepared, with good melt processing properties and significantly enhanced mechanical properties and creep resistance.

[0153] Example 9

[0154] Under vacuum, butene-1 gas was introduced into the reactor to atmospheric pressure. Then, at 50°C, 0.01 MPa of hydrogen, 0.0029 mol of triethylaluminum, 0.0024 g of 5-hexenylmethyldichlorosilane, 1 g of 1-pentene, and 30 mg of diester catalyst were added sequentially. Butene-1 gas was introduced into the reactor to 0.1 MPa, and the reaction was carried out for 10 min. The remaining butene-1 in the reactor was then vented. After the reaction was complete, the reactor was treated with excess deionized water at 100°C for 20 min. Finally, the mixture was vacuum dried at 70°C and melt-blended to obtain 10.6 g of long-chain branched 1-butene / pentene copolymer.

[0155] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and pentene content of the 1-butene / pentene copolymer prepared above were tested, and the test results are shown in Table 2.

[0156] The branched 1-butene / pentene copolymer was determined using the same method as in Example 1. 1 H-NMR spectrum, 13 C-NMR spectra, rheological properties, creep tests, and tensile mechanical tests showed that an H-type long-chain branched 1-butene / pentene copolymer was prepared, with good melt processing properties and significantly enhanced mechanical properties and creep resistance.

[0157] Comparative Example 5

[0158] The method of Example 9 was followed, except that no organosilane was added during the 1-butene / pentene copolymerization process, and 11.9g of 1-butene / pentene copolymer was finally obtained.

[0159] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and pentene content of the 1-butene / pentene copolymer prepared above were tested, and the test results are shown in Table 3.

[0160] Example 10

[0161] Under vacuum, butene-1 gas was introduced into the reactor to atmospheric pressure. Then, at 50°C, 0.01 MPa of hydrogen, 0.0029 mol of triethylaluminum, 0.0024 g of 7-octenylmethyldichlorosilane, 1 g of 1-pentene, and 30 mg of diester catalyst were added sequentially. Butene-1 gas was introduced into the reactor to 0.1 MPa, and the reaction was carried out for 10 min. The remaining butene-1 in the reactor was then vented. After the reaction was complete, the reactor was treated with excess deionized water at 100°C for 20 min. Finally, the mixture was vacuum dried at 70°C and melt-blended to obtain 10.6 g of long-chain branched 1-butene / pentene copolymer.

[0162] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and pentene content of the 1-butene / pentene copolymer prepared above were tested, and the test results are shown in Table 2.

[0163] The branched 1-butene / pentene copolymer was determined using the same method as in Example 1. 1 H-NMR spectrum, 13 C-NMR spectra, rheological properties, creep tests, and tensile mechanical tests showed that an H-type long-chain branched 1-butene / pentene copolymer was prepared, with good melt processing properties and significantly enhanced mechanical properties and creep resistance.

[0164] Example 11

[0165] Under vacuum, butene-1 gas was introduced into the reactor to atmospheric pressure. Then, at 50°C, 15 mmol of MAO, 0.0024 g of 5-hexenylmethyldichlorosilane, and 10 μmol of rac-Me2Si(2-Me-Ind)2-ZrCl2 catalyst (prepared according to US5149819; US5243001) were added sequentially. Propylene was rapidly introduced at 0.08 MPa, and then butene-1 gas was introduced into the reactor to 0.1 MPa. The reaction was allowed to proceed for 10 min. The remaining butene-1 monomer in the reactor was then vented. After the reaction was complete, the reactor was treated with deionized water at 100°C for 20 min. Finally, the reactor was vacuum dried and melt-blended at 70°C to obtain 7.8 g of long-chain branched 1-butene / propylene copolymer.

[0166] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and propylene content of the 1-butene / propylene copolymer prepared above were tested, and the test results are shown in Table 2.

[0167] The branched 1-butene / propylene copolymer was determined using the same method as in Example 1. 1 H-NMR spectrum, 13C-NMR spectra, rheological properties, creep tests, and tensile mechanical tests showed that an H-type long-chain branched 1-butene / propylene copolymer was prepared, with good melt processing properties and significantly enhanced mechanical properties and creep resistance.

[0168] Comparative Example 6

[0169] The method of Example 11 was followed, except that no organosilane was added during the 1-butene / propylene copolymerization process, and 8.2g of 1-butene / propylene copolymer was finally obtained.

[0170] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and propylene content of the 1-butene / propylene copolymer prepared above were tested, and the test results are shown in Table 3.

[0171] Example 12

[0172] Under vacuum, butene-1 gas was introduced into the reactor to atmospheric pressure. Then, at 50°C, 15 mmol of MAO, 0.0024 g of 7-octenylmethyldichlorosilane, and 10 μmol of rac-Me2Si(2-Me-Ind)2-ZrCl2 catalyst (prepared according to US5149819; US5243001) were added sequentially. Propylene was rapidly introduced at 0.08 MPa, and then butene-1 gas was introduced into the reactor to 0.1 MPa. The reaction was allowed to proceed for 10 min. The remaining butene-1 monomer in the reactor was then vented. After the reaction was complete, the reactor was treated with deionized water at 100°C for 20 min. Finally, the reactor was vacuum dried and melt-blended at 70°C to obtain 7.4 g of long-chain branched 1-butene / propylene copolymer.

[0173] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and propylene content of the 1-butene / propylene copolymer prepared above were tested, and the test results are shown in Table 2.

[0174] The branched 1-butene / propylene copolymer was determined using the same method as in Example 1. 1 H-NMR spectrum, 13 C-NMR spectra, rheological properties, creep tests, and tensile mechanical tests showed that an H-type long-chain branched 1-butene / propylene copolymer was prepared, with good melt processing properties and significantly enhanced mechanical properties and creep resistance.

[0175] Example 13

[0176] Under vacuum, butene-1 gas was introduced into the reactor to atmospheric pressure. Then, at 50°C, 15 mmol of MAO, 0.0024 g of 5-hexenylmethyldichlorosilane, and 10 μmol of rac-Me2Si(2-Me-Ind)2-ZrCl2 catalyst (prepared according to US5149819; US5243001) were added sequentially. Ethylene was rapidly introduced at 0.06 MPa, and then butene-1 gas was introduced into the reactor to 0.1 MPa. The reaction was allowed to proceed for 10 min. The remaining butene-1 monomer in the reactor was then vented. After the reaction was complete, the reactor was treated with deionized water at 100°C for 20 min. Finally, the reactor was vacuum dried and melt-blended at 70°C to obtain 7.3 g of long-chain branched 1-butene / ethylene copolymer.

[0177] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and ethylene content of the 1-butene / ethylene copolymer prepared above were tested, and the test results are shown in Table 2.

[0178] The branched 1-butene / ethylene copolymer was determined using the same method as in Example 1. 1 H-NMR spectrum, 13 C-NMR spectra, rheological properties, creep tests, and tensile mechanical tests showed that an H-type long-chain branched 1-butene / ethylene copolymer was prepared, with good melt processing properties and significantly enhanced mechanical properties and creep resistance.

[0179] Comparative Example 7

[0180] The method of Example 13 was followed, except that no organosilane was added during the 1-butene / ethylene copolymerization process, and 8.2g of 1-butene / ethylene copolymer was finally obtained.

[0181] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and ethylene content of the 1-butene / ethylene copolymer prepared above were tested, and the test results are shown in Table 3.

[0182] Example 14

[0183] Under vacuum, butene-1 gas was introduced into the reactor to atmospheric pressure. Then, at 50°C, 15 mmol of MAO, 0.0024 g of 7-octenylmethyldichlorosilane, and 10 μmol of rac-Me2Si(2-Me-Ind)2-ZrCl2 catalyst (prepared according to US5149819; US5243001) were added sequentially. Ethylene was rapidly introduced at 0.06 MPa, and then butene-1 gas was introduced into the reactor to 0.1 MPa. The reaction was allowed to proceed for 10 min. The remaining butene-1 monomer in the reactor was then vented. After the reaction was complete, the reactor was treated with deionized water at 100°C for 20 min. Finally, the reactor was vacuum dried and melt-blended at 70°C to obtain 7.1 g of long-chain branched 1-butene / ethylene copolymer.

[0184] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and ethylene content of the 1-butene / ethylene copolymer prepared above were tested, and the test results are shown in Table 2.

[0185] The branched 1-butene / ethylene copolymer was determined using the same method as in Example 1. 1 H-NMR spectrum, 13 C-NMR spectra, rheological properties, creep tests, and tensile mechanical tests showed that an H-type long-chain branched 1-butene / ethylene copolymer was prepared, with good melt processing properties and significantly enhanced mechanical properties and creep resistance.

[0186] Example 15

[0187] Under vacuum, butene-1 gas was introduced into the reactor to atmospheric pressure. Then, at 50°C, 15 mmol of MAO, 0.0024 g of 5-hexenylmethyldichlorosilane, 1 g of 1-pentene, and 10 μmol of rac-Me2Si(2-Me-Ind)2-ZrCl2 catalyst (prepared according to US5149819; US5243001) were added sequentially. Butene-1 gas was then introduced into the reactor to 0.1 MPa, and the reaction was allowed to proceed for 10 min. The remaining butene-1 monomer in the reactor was then vented. After the reaction was complete, the reactor was treated with deionized water at 100°C for 20 min. Finally, the mixture was vacuum dried at 70°C and melt-blended to obtain 6.5 g of long-chain branched 1-butene / pentene copolymer.

[0188] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and pentene content of the 1-butene / pentene copolymer prepared above were tested, and the test results are shown in Table 2.

[0189] The branched 1-butene / pentene copolymer was determined using the same method as in Example 1. 1 H-NMR spectrum, 13C-NMR spectra, rheological properties, creep tests, and tensile mechanical tests showed that an H-type long-chain branched 1-butene / pentene copolymer was prepared, with good melt processing properties and significantly enhanced mechanical properties and creep resistance.

[0190] Comparative Example 8

[0191] The method of Example 15 was followed, except that no organosilane was added during the 1-butene / pentene copolymerization process, and 8.2g of 1-butene / pentene copolymer was finally obtained.

[0192] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and pentene content of the 1-butene / pentene copolymer prepared above were tested, and the test results are shown in Table 3.

[0193] Example 16

[0194] Under vacuum, butene-1 gas was introduced into the reactor to atmospheric pressure. Then, at 50°C, 15 mmol of MAO, 0.0024 g of 7-octenylmethyldichlorosilane, 1 g of 1-pentene, and 10 μmol of rac-Me2Si(2-Me-Ind)2-ZrCl2 catalyst (prepared according to US5149819; US5243001) were added sequentially. Butene-1 gas was then introduced into the reactor to 0.1 MPa, and the reaction was allowed to proceed for 10 min. The remaining butene-1 monomer in the reactor was then vented. After the reaction was complete, the reactor was treated with deionized water at 100°C for 20 min. Finally, the mixture was vacuum dried at 70°C and melt-blended to obtain 6.5 g of long-chain branched 1-butene / pentene copolymer.

[0195] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and pentene content of the 1-butene / pentene copolymer prepared above were tested, and the test results are shown in Table 2.

[0196] The branched 1-butene / pentene copolymer was determined using the same method as in Example 1. 1 H-NMR spectrum, 13 C-NMR spectra, rheological properties, creep tests, and tensile mechanical tests showed that an H-type long-chain branched 1-butene / pentene copolymer was prepared, with good melt processing properties and significantly enhanced mechanical properties and creep resistance.

[0197] Comparative Example 9

[0198] The method of Example 1 was followed, except that the organosilane added during the 1-butene / propylene polymerization reaction was the same amount of tetramethylsilane, and 10.8g of 1-butene / propylene copolymer was finally obtained.

[0199] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and propylene content of the 1-butene / ethylene copolymer prepared above were tested, and the test results are shown in Table 4.

[0200] Comparative Example 10

[0201] The method of Example 1 was followed, except that the organosilane added during the 1-butene / propylene polymerization reaction was the same amount of tetrachlorosilane, and 10.8g of 1-butene / propylene copolymer was finally obtained.

[0202] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and propylene content of the 1-butene / ethylene copolymer prepared above were tested, and the test results are shown in Table 4.

[0203] Comparative Example 11

[0204] The method of Example 5 was followed, except that the organosilane added during the 1-butene / ethylene polymerization reaction was the same amount of tetramethylsilane, and 10.2g of 1-butene / ethylene copolymer was finally obtained.

[0205] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and ethylene content of the 1-butene / ethylene copolymer prepared above were tested, and the test results are shown in Table 4.

[0206] Comparative Example 12

[0207] The method of Example 5 was followed, except that the organosilane added during the 1-butene / ethylene polymerization reaction was the same amount of tetrachlorosilane, and 11.0 g of 1-butene / propylene copolymer was finally obtained.

[0208] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and ethylene content of the 1-butene / ethylene copolymer prepared above were tested, and the test results are shown in Table 4.

[0209] Comparative Example 13

[0210] The method of Example 9 was followed, except that the organosilane added during the 1-butene / pentene polymerization reaction was the same amount of tetramethylsilane, and 10.9g of 1-butene / pentene copolymer was finally obtained.

[0211] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and pentene content of the 1-butene / pentene copolymer prepared above were tested, and the test results are shown in Table 4.

[0212] Comparative Example 14

[0213] The method of Example 9 was followed, except that the organosilane added during the 1-butene / pentene polymerization reaction was the same amount of tetrachlorosilane, and 11.2g of 1-butene / pentene copolymer was finally obtained.

[0214] The melting temperature, storage modulus, gel content, weight-average molecular weight, Si content, and pentene content of the 1-butene / pentene copolymer prepared above were tested, and the test results are shown in Table 4.

[0215] Table 1

[0216]

[0217] Table 2

[0218]

[0219] Table 3

[0220]

[0221] Table 4

[0222]

[0223] The results in Tables 1-2 show that almost no gel is generated during the entire preparation process of the 1-butene / α-olefin copolymer. Comparing the results of Examples 1-16 and Comparative Examples 9-14, it can be seen that the organosilane provided by this invention has a different effect as a branching aid in the butene-1 polymerization process compared to silicon tetrahalides and tetraalkylsilanes. The 1-butene / α-olefin copolymer obtained using the organosilane provided by this invention exhibits higher storage modulus, elastic modulus, tensile strength, and creep resistance.

[0224] Test Example 1

[0225] The isothermal crystallization morphology of the 1-butene / propylene copolymers obtained in Example 1 and Comparative Example 1 (II-I) was observed, and the crystal transformation process was monitored. Isothermal crystallization morphology observation was performed using a BX51 polarizing microscope (POM) from Olymbus, Japan, equipped with a THMS600 hot stage from Linkam, UK. The isothermal crystallization temperature was 88°C. Figure 3 As shown, with the extension of isothermal time, crystal nuclei appear and gradually grow, and spherical crystals are compressed and stacked together. Compared with Comparative Example 1, under the same crystallization time, more crystal nuclei can be observed in the field of view in Example 1, and the size of the spherical crystals is significantly reduced, indicating stronger crystallization ability. The crystal transformation process was monitored using a Rigaku D / max 2500 wide-angle X-ray diffractometer (Japan). The laser source was Cu Kα, the wavelength was 0.154 nm, the scanning speed was 2° / min, and the scanning range was 5° to 30°. Figure 4To monitor the II-I crystal transformation process of the H-type long-chain branched 1-butene / propylene copolymer of Example 1 and the 1-butene / propylene copolymer of Comparative Example 1, by... Figure 4 The initial XRD characterization of the sample showed distinct peaks at 2θ = 11.9, 16.9, and 18.5°, corresponding to the (200), (220), and (213) crystal planes of type II, respectively. This confirms that melt crystallization only produces crystal type II, which has a kinetic advantage. After room temperature annealing, peaks at 2θ = 9.9, 17.5, and 20.4° appeared in the XRD characterization, corresponding to the (110), (300), and (220) crystal planes of type I, respectively. It can be observed that the intensity of the primary diffraction peaks of type II crystals decreases with increasing annealing time, while the intensity of the primary diffraction peaks of type I crystals increases. This proves that all samples underwent a certain degree of crystal transformation, but the transformation rates differed significantly.

[0226] To quantify the rate of the II-I type crystal transition, the proportion of type I crystals in the total number of crystals (f) I The proportion can be calculated by the following formula, where A(110) and A(200) are the integral areas of the characteristic diffraction peaks of type I crystal (110) and type II crystal (200), respectively. The correction parameter R used is 0.36, and the results are as follows: Figure 5 As shown, it can be observed that the H-type long-chain branched 1-butene / propylene copolymer obtained by the present invention significantly accelerates the crystal transformation process, and can be completely transformed within 8 hours, which greatly shortens the production cycle of the sample.

[0227]

[0228] Creep tests were conducted using TA's DMA800, employing a three-point bending mode, with a set temperature of 80℃ and a stress of 8MPa. Figure 6 The creep test results of the H-type long-chain branched 1-butene / propylene copolymer of Example 1 and the 1-butene / propylene copolymer of Comparative Example 1 show that after stress is applied, the deformation generated in Example 1 is much lower than that in Comparative Example 1. After the stress is removed, the final irreversible deformation generated in Example 1 is also much lower than that in Comparative Example 1, which proves that the creep resistance of Example 1 is significantly improved compared with Comparative Example 1.

[0229] The tensile mechanical properties of the prepared 1-butene / α-olefin copolymer were tested using a universal tensile testing machine from Instron Corporation, USA. Figure 7 Mechanical tests were conducted on the H-type long-chain branched 1-butene / propylene copolymer of Example 1 and the 1-butene / propylene copolymer of Comparative Example 1. The results showed that, compared with Comparative Example 1, the elastic modulus, tensile strength, and breaking strength of Example 1 were significantly improved, indicating enhanced mechanical properties.

[0230] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications all fall within the protection scope of the present invention. Furthermore, various different embodiments of the present invention can also be arbitrarily combined, as long as they do not violate the spirit of the present invention, they should also be considered as the content disclosed by the present invention.

Claims

1. A 1-butene / α-olefin copolymer, characterized in that, The 1-butene / α-olefin copolymer contains a structure in which ω-olefinic dihalosilane is inserted into the main chain of the 1-butene / α-olefin copolymer, and the molar percentage of Si atoms in the 1-butene / α-olefin copolymer is 0.0001‰-1‰.

2. The 1-butene / α-olefin copolymer according to claim 1, wherein, The 1-butene / α-olefin copolymer contains an H-type long-chain branched structure as shown in formula (I). In the formula, n is an integer from 0 to 10, k is an integer from 0 to 18, R is a hydrogen atom or a C1-C3 alkyl group, and R1 is a C2-C3 alkyl group. 20 α-olefinic group, R2 is C1-C 20 Straight-chain, branched, or isomerized alkyl groups, It is the backbone of a 1-butene / α-olefin copolymer.

3. The 1-butene / α-olefin copolymer according to claim 1, wherein, The ω-olefinic dihalosilane is selected from general formula R. 1 SiX2R 2 At least one of the compounds with the structure shown, in the general formula, R 1 An olefinic group with 2-20 carbon atoms and a terminal olefinic double bond, R 2 X is a straight-chain, branched, or isomerized alkyl group having 1-20 carbon atoms, and X is a halogen; Preferably, the ω-olefinic dihalosilane is 11-dodecenylmethyldichlorosilane, 11-dodecenylethyldichlorosilane, 11-dodecenylisopropyldichlorosilane, 9-decenylmethyldichlorosilane, 9-decenylethyldichlorosilane, 9-decenylbutyldichlorosilane, 8-nonenylmethyldichlorosilane, 8-nonenylethyldichlorosilane, 7-octenylmethyldichlorosilane, 7-octenylethyldichlorosilane, 7-octenyl... At least one of 1, 6-heptenylmethyldichlorosilane, 6-heptenylethyldichlorosilane, 5-hexenylmethyldichlorosilane, 5-hexenylethyldichlorosilane, 4-pentenylmethyldichlorosilane, 4-pentenylethyldichlorosilane, 3-butenylmethyldichlorosilane, 3-butenylethyldichlorosilane, 7-octenylcyclohexyldichlorosilane, 5-hexenylcyclohexyldichlorosilane, and 3-butenylcyclohexyldichlorosilane; Preferably, the weight-average molecular weight of the 1-butene / α-olefin copolymer is 1×10⁻⁶. 3 ~2×10 7 g / mol, preferably 1×10 4 -1×10 6 g / mol; Preferably, the molecular weight distribution of the 1-butene / α-olefin copolymer is 2-20, more preferably 2-10.

4. The 1-butene / α-olefin copolymer according to any one of claims 1-3, wherein, Based on the total molar number of the 1-butene and the α-olefin monomer, the α-olefin monomer content in the 1-butene / α-olefin copolymer is 1-20 mol%, preferably 4-10 mol%. The α-olefin monomer is at least one of ethylene, propylene, and 1-pentene.

5. A method for preparing a 1-butene / α-olefin copolymer, characterized in that, The method includes: performing a copolymerization reaction of butene-1 and α-olefin monomers in the presence of ω-olefin dihalosilane under the action of a catalyst, and subjecting the polymer product to water treatment, drying and melt mixing, wherein the catalyst is a Ziegler-Natta catalyst or a metallocene catalyst.

6. The method according to claim 5, wherein, The ω-olefinic dihalosilane is selected from general formula R. 1 SiX2R 2 At least one of the compounds with the structure shown, in the general formula, R 1 An olefinic group with 2-20 carbon atoms and a terminal olefinic double bond, R 2 X is a straight-chain, branched, or isomerized alkyl group having 1-20 carbon atoms, and X is a halogen; Preferably, the ω-olefinic dihalosilane is 11-dodecenylmethyldichlorosilane, 11-dodecenylethyldichlorosilane, 11-dodecenylisopropyldichlorosilane, 9-decenylmethyldichlorosilane, 9-decenylethyldichlorosilane, 9-decenylbutyldichlorosilane, 8-nonenylmethyldichlorosilane, 8-nonenylethyldichlorosilane, 7-octenylmethyldichlorosilane, 7-octenylethyldichlorosilane, 7-octenyl... At least one of 1, 6-heptenylmethyldichlorosilane, 6-heptenylethyldichlorosilane, 5-hexenylmethyldichlorosilane, 5-hexenylethyldichlorosilane, 4-pentenylmethyldichlorosilane, 4-pentenylethyldichlorosilane, 3-butenylmethyldichlorosilane, 3-butenylethyldichlorosilane, 7-octenylcyclohexyldichlorosilane, 5-hexenylcyclohexyldichlorosilane, and 3-butenylcyclohexyldichlorosilane.

7. The method according to claim 5, wherein, Based on the total molar number of the 1-butene and the α-olefin monomer, the content of the α-olefin monomer is 1-20 mol%, preferably 4-10 mol%. The α-olefin monomer is at least one of ethylene, propylene, and 1-pentene.

8. The method according to any one of claims 5-7, wherein, The total amount of the ω-olefinic dihalosilane is 0.001-0.2 parts by weight relative to 100 parts by weight of the polymerization monomer.

9. The method according to any one of claims 5-7, wherein, The Ziegler-Natta catalyst is a MgCl2 supported catalytic system, which contains MgCl2, TiCl4, alkyl aluminum, and selectively contained internal and / or external electron donors. Preferably, the co-catalyst of the Ziegler-Natta catalyst is alkylaluminum, the internal electron donor of the Ziegler-Natta catalyst is one of aromatic carboxylic acid monoesters, aromatic carboxylic acid diesters, diethers, succinates, diol esters, etc., and the external electron donor of the Ziegler-Natta catalyst is at least one of alkoxysilane compounds. Preferably, the molar ratio of the organoaluminum compound to the external electron donor in the Ziegler-Natta catalyst is 1:1-200:1 in terms of aluminum / silicon ratio, more preferably 10:1-50:

1.

10. The method according to any one of claims 5-7, wherein, The metallocene catalyst has a Cp m R n MX q Organometallic compounds with the structure Cp being independently substituted or unsubstituted cyclopentadienyl groups and their derivatives; M being a group 4, 5, or 6 transition metal; R being a structural bridge providing stereorigor between two Cp groups; X being a halogen or a hydrocarbon group having 1-20 carbon atoms; and m = 1-2, n = 0-1, q = 2-3, the sum of m+q being equal to the oxidation state of the transition metal; Preferably, the polymerization is carried out in the presence of a co-catalyst selected from alkylaluminoxane compounds or organoborides.

11. The method according to any one of claims 5-7, wherein, The polymerization reaction is carried out in the presence of hydrogen gas; Preferably, in the polymerization reaction, the amount of hydrogen gas used is 10 parts by weight or less relative to 100 parts by weight of the polymerization monomer.

12. The method according to any one of claims 5-7, wherein, The conditions for the polymerization reaction include: a polymerization temperature of 0-100℃ and a polymerization time of 0.05-5 hours; Preferably, the polymerization reaction is carried out at a pressure of 0.1-10 atmospheres; Preferably, the water treatment conditions include a temperature of 50-120°C and a time of 0.2-12 hours; more preferably, the treatment conditions include a temperature of 70-110°C and a time of 0.25-2 hours.

13. The 1-butene / α-olefin copolymer prepared by the method of any one of claims 5-12.

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