Catalytic system for olefin copolymerization and application

Abstract

The application provides a catalytic system for olefin copolymerization and application, and the catalytic system comprises a main catalyst, an aluminum-containing cocatalyst and an electron donor; wherein a structural formula of the electron donor is shown as formula I: formula I The catalytic system of the application can be used for olefin copolymerization, and can prepare an olefin copolymer material with excellent self-repairing performance.

Description

Technical Field

[0001] This invention relates to the field of polyolefin catalyst technology, and more specifically to a catalytic system for olefin copolymerization and its application. Background Technology

[0002] During use, external impacts, wear and other factors can cause scratches and cracks in polymer materials. These damages greatly limit the service life and safety of polymer materials. Therefore, designing and developing self-healing polymer materials with damage repair capabilities is of great value for extending material life, improving safety, reducing maintenance costs, and achieving recycling.

[0003] Self-healing polymer materials can be divided into two systems: extrinsic self-healing materials and intrinsic self-healing materials. Extrinsic self-healing materials have a limited number of repair cycles and their self-healing function needs improvement, thus limiting their application. Intrinsic self-healing materials are designed and prepared by introducing reversible dynamic bonds into the structure. However, existing intrinsic self-healing materials suffer from problems such as requiring heating for repair, long repair times, and low repair efficiency. For example, patent document ZL202410016171.7 discloses a method for preparing a functionalized intrinsic self-healing polymer. This document discloses a free radical polymerization reaction of methyl methacrylate, butyl acrylate, and vinyl monomers containing imidazole, carboxyl, and hydroxyl functional groups, with a molar ratio of 32:48:10 for the three monomers, resulting in a material with good mechanical and self-healing properties. However, the polymer prepared in this document only achieves a repair efficiency of approximately 50% after 24 hours of repair at room temperature. Patent document ZL202310610507 discloses a self-healing elastomer based on triple hydrogen bonding and metal coordination, and its preparation method. Specifically, it discloses an imidazole-functionalized trimesoamide (BTA) molecule and an imidazole-functionalized acrylate polymer, and uses a metal salt to coordinate and crosslink them to obtain a self-healing polymer elastomer material exhibiting good mechanical properties, with a maximum tensile strength of 10 MPa and an elongation at break of 2000%. However, the method provided in this document is complex and costly. Patent document ZL20241034015... 9.1 discloses a functional vinyl olefin polymer and its preparation method, comprising the following steps: S) under anhydrous and oxygen-free conditions, ethylene, α-olefin, olefin siloxane monomer, copolymerization catalyst, co-catalyst and organic solvent are mixed and heated to carry out a polymerization reaction to obtain the functional vinyl olefin polymer; the copolymerization catalyst is a monometallocene catalyst containing zirconium or a post-metallocene catalyst containing zirconium; Patent document ZL202410050193.5 discloses an IVB group metal complex and its preparation method and application, specifically disclosing a class of O^O^O^O coordinated IVB group metal complexes, and its application in catalyzing the copolymerization of ethylene and α-olefins.

[0004] Improving the self-healing function of olefin copolymers has become a research hotspot in the field. Summary of the Invention

[0005] This invention provides a catalytic system and its application for olefin copolymerization, which can be used to catalyze olefin copolymerization reactions and prepare olefin copolymer products with excellent self-healing properties.

[0006] This invention provides a catalytic system for olefin copolymerization, the catalytic system comprising a main catalyst, an aluminum-containing co-catalyst, and an electron donor; wherein the electron donor has the structural formula shown in Formula I:

[0007] Formula I

[0008] In Formula I, R is selected from substituted or unsubstituted C1-C6 alkyl, C1-C6 alkoxy, C3-C10 cycloalkyl, 3-10 membered heterocyclic, C3-10 cycloalkyloxy, C6-C20 aryl, or C6-C20 aryloxy groups. 1 R 2 R 3 R 4 R 5 Each is independently selected from hydrogen, halogen, substituted or unsubstituted C1-C6 alkyl, C1-C6 alkoxy, C3-C10 cycloalkyl, 3-10 heterocyclic, C3-C10 cycloalkyloxy, C6-C20 aryl or C6-C20 aryloxy, wherein the substituents of the substituted C1-C6 alkyl include C6-C20 aryl.

[0009] Optionally, the main catalyst is selected from CpMX3 or MY. n Wherein, Cp is selected from cyclopentadienyl or pentamethylcyclopentadiene, X includes one or more of halogens and methyl groups, Y includes one or more of acetylacetone, tert-butoxy, and n-butoxy groups, n is 3 or 4, and M is a group IVB transition metal; and / or, the aluminum-containing cocatalyst includes one or more of alkylaluminum cocatalysts, alkylaluminum chloride cocatalysts, and alkoxyaluminum cocatalysts.

[0010] Optionally, the molar ratio of the electron donor to the main catalyst is (2~10):1; and / or, the molar ratio of the aluminum-containing co-catalyst to the main catalyst is (5~1500):1; and / or, M includes one or more of titanium, zirconium, and hafnium.

[0011] Optionally, the electron donor is prepared by a method comprising at least the following steps: adding a compound of Formula II to a starting material system comprising substituted or unsubstituted arylphosphoric acid, a first organic solvent, and a second organic solvent, and then reacting the reaction system at 30–80°C to obtain the electron donor; wherein the compound of Formula II is shown below.

[0012] Formula II

[0013] In Formula II, X includes halogens; the substituents in the substituted aryl phosphates include R. 1 R 2 R 3 R 4 R 5 The first organic solvent includes one or more of cyclohexanoic acid, hexanoic acid, butyric acid, acrylic acid, benzoic acid, and pyridine; the second organic solvent includes one or more of dichloromethane and acetone.

[0014] Optionally, the electron donor includes phenyl phosphite, (p-tolyl) phenyl phosphite, (p-ethylphenyl) phenyl phosphite, (p-isopropylphenyl) phenyl phosphite, (p-tert-butylphenyl) phenyl phosphite, (4-fluorophenyl) phenyl phosphite, (4-chlorophenyl) phenyl phosphite, (4-bromophenyl) phenyl phosphite, (4-trifluoromethylphenyl) phenyl phosphite, (4-methoxyphenyl) phenyl phosphite, (4-trifluoromethoxyphenyl) phenyl phosphite, (4-nitrophenyl) phenyl phosphite, (o-tolyl) phenyl phosphite, (o-ethylphenyl) phenyl phosphite, (o-isopropylphenyl) phenyl phosphite, (o-tert-butylphenyl) phenyl phosphite, (2-fluorophenyl) phenyl phosphite, and (2-chlorophenyl) phenyl phosphite. Ester, (2-bromophenyl) phenyl phosphite, (2-trifluoromethylphenyl) phenyl phosphite, (2-methoxyphenyl) phenyl phosphite, (2-trifluoromethoxyphenyl) phenyl phosphite, (2-nitrophenyl) phenyl phosphite, (m-tolyl) phenyl phosphite, (m-ethylphenyl) phenyl phosphite, (m-isopropylphenyl) phenyl phosphite, (m-tert-butylphenyl) phenyl phosphite, (3-fluorophenyl) phenyl phosphite, (3-chlorophenyl) phenyl phosphite, (3-bromophenyl) phenyl phosphite, (3-trifluoromethylphenyl) phenyl phosphite, (3-methoxyphenyl) phenyl phosphite, (3-trifluoromethoxyphenyl) phenyl phosphite, (3-nitrophenyl) phenyl phosphite, naphthyl phenyl phosphite, thiophene phenyl phosphite, pyridyl Phenyl phosphite, styryl phenyl phosphite, phenyl phosphite ethyl ester, (p-tolyl) phosphite ethyl ester, (p-ethylphenyl) phosphite ethyl ester, (p-isopropylphenyl) phosphite ethyl ester, (p-tert-butylphenyl) phosphite ethyl ester, (4-fluorophenyl) phosphite ethyl ester, (4-chlorophenyl) phosphite ethyl ester, (4-bromophenyl) phosphite ethyl ester, (4-trifluoromethylphenyl) phosphite ethyl ester, (4-methoxyphenyl) phosphite ethyl ester, (4-trifluoromethoxyphenyl) phosphite ethyl ester, (4-nitrophenyl) phosphite ethyl ester, (o-tolyl) phosphite ethyl ester, (o-ethylphenyl) phosphite ethyl ester, (o-isopropylphenyl) phosphite ethyl ester, (o-tert-butylphenyl) phosphite ethyl ester, (2-fluorophenyl) phosphite ethyl ester, (2-chlorophenyl) phosphite ethyl ester Ethyl phosphate, (2-bromophenyl) phosphite, (2-trifluoromethylphenyl) phosphite, (2-methoxyphenyl) phosphite, (2-trifluoromethoxyphenyl) phosphite, (2-nitrophenyl) phosphite, (m-tolyl) phosphite, (m-ethylphenyl) phosphite, (m-isopropylphenyl) phosphite, (m-tert-butylphenyl) phosphite, (3-fluorophenyl) phosphite, (3-chlorophenyl) phosphite, (3-bromophenyl) phosphite, (3-trifluoromethylphenyl) phosphite, (3-methoxyphenyl) phosphite, (3-trifluoromethoxyphenyl) phosphite, (3-nitrophenyl) phosphite, naphthyl phosphite, thiophene phosphite,Ethyl pyridyl phosphite, ethyl styryl phosphite, butyl phenyl phosphite, butyl (p-tolyl) phosphite, butyl (p-ethylphenyl) phosphite, butyl (p-isopropylphenyl) phosphite, butyl (p-tert-butylphenyl) phosphite, butyl (4-fluorophenyl) phosphite, butyl (4-chlorophenyl) phosphite, butyl (4-bromophenyl) phosphite, butyl (4-trifluoromethylphenyl) phosphite, butyl (4-methoxyphenyl) phosphite, butyl (4-trifluoromethoxyphenyl) phosphite, butyl (4-nitrophenyl) phosphite, butyl (o-tolyl) phosphite, butyl (o-ethylphenyl) phosphite, butyl (o-isopropylphenyl) phosphite, butyl (o-tert-butylphenyl) phosphite, butyl (2-fluorophenyl) phosphite, butyl (2-chlorophenyl) phosphite... (Phenyl) phosphite butyl ester, (2-bromophenyl) phosphite butyl ester, (2-trifluoromethylphenyl) phosphite butyl ester, (2-methoxyphenyl) phosphite butyl ester, (2-trifluoromethoxyphenyl) phosphite butyl ester, (2-nitrophenyl) phosphite butyl ester, (m-tolyl) phosphite butyl ester, (m-ethylphenyl) phosphite butyl ester, (m-isopropylphenyl) phosphite butyl ester, (m-tert-butylphenyl) phosphite butyl ester, (3-fluorophenyl) phosphite butyl ester, (3-chlorophenyl) phosphite butyl ester, (3-bromophenyl) phosphite butyl ester, (3-trifluoromethylphenyl) phosphite butyl ester, (3-methoxyphenyl) phosphite butyl ester, (3-trifluoromethoxyphenyl) phosphite butyl ester, (3-nitrophenyl) phosphite butyl ester, naphthyl phosphite butyl ester, thiophene Butyl phosphate, pyridyl phosphite, styryl phosphite, phenyl octyl phosphite, (p-tolyl) octyl phosphite, (p-ethylphenyl) octyl phosphite, (p-isopropylphenyl) octyl phosphite, (p-tert-butylphenyl) octyl phosphite, (4-fluorophenyl) octyl phosphite, (4-chlorophenyl) octyl phosphite, (4-bromophenyl) octyl phosphite, (4-trifluoromethylphenyl) octyl phosphite, (4-methoxyphenyl) octyl phosphite, (4-trifluoromethoxyphenyl) octyl phosphite, (4-nitrophenyl) octyl phosphite, (o-tolyl) octyl phosphite, (o-ethylphenyl) octyl phosphite, (o-isopropylphenyl) octyl phosphite, (o-tert-butylphenyl) octyl phosphite, (2-fluorophenyl) octyl phosphite Octyl (2-chlorophenyl) phosphite, Octyl (2-bromophenyl) phosphite, Octyl (2-trifluoromethylphenyl) phosphite, Octyl (2-methoxyphenyl) phosphite, Octyl (2-trifluoromethoxyphenyl) phosphite, Octyl (2-nitrophenyl) phosphite, Octyl (m-tolyl) phosphite, Octyl (m-ethylphenyl) phosphite, Octyl (m-isopropylphenyl) phosphite, Octyl (m-tert-butylphenyl) phosphite, Octyl (3-fluorophenyl) phosphite, Octyl (3-chlorophenyl) phosphite, Octyl (3-bromophenyl) phosphite, Octyl (3-trifluoromethylphenyl) phosphite, Octyl (3-methoxyphenyl) phosphite, Octyl (3-trifluoromethoxyphenyl) phosphite, Octyl (3-nitrophenyl) phosphite, Octyl naphthyl phosphite, Octyl (naphthyl) phosphiteOne or more of thienyl phosphite octyl ester, pyridyl phosphite octyl ester, and styryl phosphite octyl ester.

[0015] The present invention provides a method for preparing an olefin block copolymer, comprising: subjecting isoprene and styrene to an olefin copolymerization reaction under the action of a catalytic system as described above, to prepare the olefin block copolymer.

[0016] Optionally, the temperature of the olefin copolymerization reaction is -20 to 90°C, preferably 20 to 80°C; and / or, the pressure of the olefin copolymerization reaction is 1 to 10 standard atmospheres, preferably 1 to 7 standard atmospheres; and / or, the time of the olefin copolymerization reaction is 0.05 to 10 hours, preferably 0.5 to 2 hours; and / or, the molar ratio of isoprene to styrene is 0.3 to 0.7.

[0017] The present invention provides an olefin block copolymer, which is obtained by the preparation method described above.

[0018] Optionally, the olefin block copolymer comprises 50% to 70% crystalline hard segments and 30% to 50% amorphous soft segments in molar percentage, wherein the crystalline hard segments include polystyrene segments and the amorphous soft segments include polyisoprene segments.

[0019] Optionally, the olefin block copolymer has a glass transition temperature of -30 to 0°C, a weight-average molecular weight of 125 to 670 kDa, a molecular weight distribution index of 2.0 to 2.5, a tensile strength of 6.0 to 22.0 MPa, and an elongation at break of 130% to 550%.

[0020] This invention provides a catalytic system and its application for olefin copolymerization. By providing an electron donor with a special structure, and combining the electron donor, a main catalyst, and an aluminum-containing co-catalyst to form a catalytic system, this catalytic system can be used to prepare olefin block copolymers through olefin copolymerization. When the olefin block copolymer (self-healing polyolefin material) is damaged, it can quickly achieve self-repair after docking at room temperature without the need for external adhesives. The repair efficiency is high, and the repair process is simple. Furthermore, the self-healing polyolefin material also has good mechanical properties. In addition, it can simplify the olefin copolymerization process. Attached Figure Description

[0021] Figure 1 This is a schematic diagram showing the segment distribution and molar percentage content in an olefin block copolymer according to an embodiment of the present invention. Figure 1 In this context, the crystallizable segment is the same as the crystalline hard segment. Detailed Implementation

[0022] To enable those skilled in the art to better understand the present invention, the present invention will be further described in detail below. The specific embodiments listed below are merely descriptions of the principles and features of the present invention, and the examples are only for explaining the present invention and are not intended to limit the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0023] The self-healing function of olefin copolymers in the prior art needs to be improved. The inventors found in their research that the self-healing function of olefin copolymers can be improved by improving the catalytic system of olefin copolymerization.

[0024] Based on this, embodiments of the present invention provide a catalytic system for olefin copolymerization, the catalytic system comprising a main catalyst, an aluminum-containing co-catalyst, and an electron donor; wherein the structural formula of the electron donor is shown in Formula I:

[0025] Formula I

[0026] In Formula I, R is selected from substituted or unsubstituted C1-C6 alkyl, C1-C6 alkoxy, C3-C10 cycloalkyl, 3-10 membered heterocyclic, C3-10 cycloalkyloxy, C6-C20 aryl, or C6-C20 aryloxy groups. 1 R 2 R 3 R 4 R 5 Each is independently selected from hydrogen, halogen, substituted or unsubstituted C1-C6 alkyl, C1-C6 alkoxy, C3-C10 cycloalkyl, 3-10 heterocyclic, C3-C10 cycloalkyloxy, C6-C20 aryl or C6-C20 aryloxy, wherein the substituents of the substituted C1-C6 alkyl include C6-C20 aryl.

[0027] According to the inventors' research and analysis, under the above-mentioned catalytic system, the electron donor, main catalyst, and aluminum-containing co-catalyst work synergistically to enable the steric hindrance and electronic effects of the electron donor to influence the coordination space and electron cloud density near the metal active center. In the olefin copolymerization process, by regulating the catalytic active center through the external electron donor, more styrene monomers can be inserted into the olefin copolymer to form hard segment crystalline regions, achieve microphase separation, and thus improve the self-healing function of the olefin copolymer.

[0028] Specifically, in Formula I, the substituted C1-C6 alkyl may include C6-C20 aryl-substituted C1-C6 alkyl (C6-20 aryl C1-6 alkyl) and / or diC6-C20 aryl-substituted C1-C6 alkyl (diC6-20 aryl C1-6 alkyl).

[0029] Figure 1 This is a schematic diagram showing the segment distribution and molar percentage content in an olefin block copolymer according to an embodiment of the present invention. Figure 1 In this context, the crystallizable segment is the same as the crystalline hard segment.

[0030] In some embodiments, the main catalyst is selected from CpMX3 or MY. n In this context, Cp is selected from cyclopentadienyl or pentamethylcyclopentadiene, X includes one or more of halogens and methyl groups, Y includes one or more of acetylacetonyl, tert-butoxy, and n-butoxy groups, n is 3 or 4, and M is a group IVB transition metal.

[0031] The M mentioned above may include one or more of titanium, zirconium, and hafnium.

[0032] Furthermore, the main catalyst can be selected from CpTiX3 or TiY. n Wherein, Cp includes cyclopentadienyl (C5H5), X includes chlorine (Cl) and / or fluorine (F), or Cp includes pentamethylcyclopentadiene (C5Me5), X includes methyl (Me); Y includes acetylacetonyl (acac), n is 3, or Y includes tert-butoxy (O-tert-Bu), n is 4.

[0033] Preferably, the main catalyst may include tetra-n-butoxytitanium (Ti(OBu)4).

[0034] The aforementioned aluminum-containing cocatalyst may include one or more of alkyl aluminum cocatalysts, alkyl aluminum chloride cocatalysts, and alkoxy aluminum cocatalysts, with alkoxy aluminum cocatalysts being preferred (e.g., modified methylaluminoxane MMAO is preferred).

[0035] In some embodiments, the molar ratio of electron donor to main catalyst is (2~10):1, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1 or any combination thereof, preferably 5:1.

[0036] In addition, the molar ratio of aluminum-containing co-catalyst to main catalyst can be (5~1000):1, preferably 500:1.

[0037] In some embodiments, the above-mentioned electron donor can be prepared by a method comprising at least the following processes:

[0038] By adding the compound represented by Formula II to a starting material system comprising substituted or unsubstituted arylphosphoric acid, a first organic solvent, and a second organic solvent, and then reacting the system at 30–80 °C, an electron donor is obtained; wherein the compound represented by Formula II is shown below.

[0039] Formula II

[0040] In Formula II, X includes halogens (e.g., chlorine); the substituents in the substituted aryl phosphates include the aforementioned R. 1 R 2 R 3 R 4 R 5 ;

[0041] The first organic solvent (weak acid) includes one or more of cyclohexanoic acid, hexanoic acid, butyric acid, acrylic acid, benzoic acid, and pyridine, preferably hexanoic acid; the second organic solvent (non-polar solvent) includes one or more of dichloromethane and acetone, preferably dichloromethane.

[0042] In practice, the compound (R) shown in Formula II above can be placed in a double-necked round-bottom flask (e.g., a 100 mL double-necked round-bottom flask). 1 R 2 R 3 R 4 R 5 A reactant system is obtained by mixing a substituted arylphosphoric acid, a first organic solvent (weak acid), and a second organic solvent (nonpolar solvent); a solution comprising the compound shown in Formula III is then added dropwise to the reactant system to obtain a reaction system; the reaction system is then subjected to a reaction at 30–80°C, for example, by reflux; after 2–8 hours of reaction, an inorganic acid solution is added to the reaction system; the organic phase is then collected (e.g., separated and collected using a separatory funnel), washed with deionized water, dried (e.g., dried with anhydrous sodium sulfate), and the solvent is removed; the mixture is then purified by column chromatography to obtain the electron donor. Exemplarily, the reaction temperature can be 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, or any combination thereof, preferably 30–50°C. Furthermore, the reaction time is preferably 2–4 hours.

[0043] Furthermore, the solution comprising the compound shown in Formula II can be obtained by dissolving the compound shown in Formula II in an organic solvent (e.g., dichloromethane).

[0044] In some embodiments, the compound represented by Formula II above includes one or more of phenyl chloroformate and octyl chloroformate.

[0045] Furthermore, the inorganic acid in the above-mentioned inorganic acid solution may include one or more of hydrochloric acid, sulfuric acid, and nitric acid, preferably sulfuric acid; further, the above-mentioned inorganic acid solution may include one or more of hydrochloric acid aqueous solution, sulfuric acid aqueous solution, and nitric acid aqueous solution; even further, the above-mentioned inorganic acid solution (dilute inorganic acid solution) may include one or more of hydrochloric acid aqueous solution, sulfuric acid aqueous solution, and nitric acid aqueous solution with a concentration of 0.1M.

[0046] The column chromatography described above can be performed using rapid column chromatography. The eluent used in the column chromatography may include a mixed solution of dichloromethane and ethyl acetate, with a volume ratio of dichloromethane to ethyl acetate of (5~6):1.

[0047] Specifically, the electron donors mentioned above include phenyl phosphite, (p-tolyl)phenyl phosphite, (p-ethylphenyl)phenyl phosphite, (p-isopropylphenyl)phenyl phosphite, (p-tert-butylphenyl)phenyl phosphite, (4-fluorophenyl)phenyl phosphite, (4-chlorophenyl)phenyl phosphite, (4-bromophenyl)phenyl phosphite, (4-trifluoromethylphenyl)phenyl phosphite, (4-methoxyphenyl)phenyl phosphite, (4-trifluoromethoxyphenyl)phenyl phosphite, (4-nitrophenyl)phenyl phosphite, (o-tolyl)phenyl phosphite, (o-ethylphenyl)phenyl phosphite, (o-isopropylphenyl)phenyl phosphite, (o-tert-butylphenyl)phenyl phosphite, (2-fluorophenyl)phenyl phosphite, and (2-chlorophenyl)phenyl phosphite. Ester, (2-bromophenyl) phenyl phosphite, (2-trifluoromethylphenyl) phenyl phosphite, (2-methoxyphenyl) phenyl phosphite, (2-trifluoromethoxyphenyl) phenyl phosphite, (2-nitrophenyl) phenyl phosphite, (m-tolyl) phenyl phosphite, (m-ethylphenyl) phenyl phosphite, (m-isopropylphenyl) phenyl phosphite, (m-tert-butylphenyl) phenyl phosphite, (3-fluorophenyl) phenyl phosphite, (3-chlorophenyl) phenyl phosphite, (3-bromophenyl) phenyl phosphite, (3-trifluoromethylphenyl) phenyl phosphite, (3-methoxyphenyl) phenyl phosphite, (3-trifluoromethoxyphenyl) phenyl phosphite, (3-nitrophenyl) phenyl phosphite, naphthyl phenyl phosphite, thiophene phenyl phosphite, pyridyl Phenyl phosphite, styryl phenyl phosphite, phenyl phosphite ethyl ester, (p-tolyl) phosphite ethyl ester, (p-ethylphenyl) phosphite ethyl ester, (p-isopropylphenyl) phosphite ethyl ester, (p-tert-butylphenyl) phosphite ethyl ester, (4-fluorophenyl) phosphite ethyl ester, (4-chlorophenyl) phosphite ethyl ester, (4-bromophenyl) phosphite ethyl ester, (4-trifluoromethylphenyl) phosphite ethyl ester, (4-methoxyphenyl) phosphite ethyl ester, (4-trifluoromethoxyphenyl) phosphite ethyl ester, (4-nitrophenyl) phosphite ethyl ester, (o-tolyl) phosphite ethyl ester, (o-ethylphenyl) phosphite ethyl ester, (o-isopropylphenyl) phosphite ethyl ester, (o-tert-butylphenyl) phosphite ethyl ester, (2-fluorophenyl) phosphite ethyl ester, (2-chlorophenyl) phosphite ethyl ester Ethyl phosphate, (2-bromophenyl) phosphite, (2-trifluoromethylphenyl) phosphite, (2-methoxyphenyl) phosphite, (2-trifluoromethoxyphenyl) phosphite, (2-nitrophenyl) phosphite, (m-tolyl) phosphite, (m-ethylphenyl) phosphite, (m-isopropylphenyl) phosphite, (m-tert-butylphenyl) phosphite, (3-fluorophenyl) phosphite, (3-chlorophenyl) phosphite, (3-bromophenyl) phosphite, (3-trifluoromethylphenyl) phosphite, (3-methoxyphenyl) phosphite, (3-trifluoromethoxyphenyl) phosphite, (3-nitrophenyl) phosphite, naphthyl phosphite, thiophene phosphite,Ethyl pyridyl phosphite, ethyl styryl phosphite, butyl phenyl phosphite, butyl (p-tolyl) phosphite, butyl (p-ethylphenyl) phosphite, butyl (p-isopropylphenyl) phosphite, butyl (p-tert-butylphenyl) phosphite, butyl (4-fluorophenyl) phosphite, butyl (4-chlorophenyl) phosphite, butyl (4-bromophenyl) phosphite, butyl (4-trifluoromethylphenyl) phosphite, butyl (4-methoxyphenyl) phosphite, butyl (4-trifluoromethoxyphenyl) phosphite, butyl (4-nitrophenyl) phosphite, butyl (o-tolyl) phosphite, butyl (o-ethylphenyl) phosphite, butyl (o-isopropylphenyl) phosphite, butyl (o-tert-butylphenyl) phosphite, butyl (2-fluorophenyl) phosphite, butyl (2-chlorophenyl) phosphite... (Phenyl) phosphite butyl ester, (2-bromophenyl) phosphite butyl ester, (2-trifluoromethylphenyl) phosphite butyl ester, (2-methoxyphenyl) phosphite butyl ester, (2-trifluoromethoxyphenyl) phosphite butyl ester, (2-nitrophenyl) phosphite butyl ester, (m-tolyl) phosphite butyl ester, (m-ethylphenyl) phosphite butyl ester, (m-isopropylphenyl) phosphite butyl ester, (m-tert-butylphenyl) phosphite butyl ester, (3-fluorophenyl) phosphite butyl ester, (3-chlorophenyl) phosphite butyl ester, (3-bromophenyl) phosphite butyl ester, (3-trifluoromethylphenyl) phosphite butyl ester, (3-methoxyphenyl) phosphite butyl ester, (3-trifluoromethoxyphenyl) phosphite butyl ester, (3-nitrophenyl) phosphite butyl ester, naphthyl phosphite butyl ester, thiophene Butyl phosphate, pyridyl phosphite, styryl phosphite, phenyl octyl phosphite, (p-tolyl) octyl phosphite, (p-ethylphenyl) octyl phosphite, (p-isopropylphenyl) octyl phosphite, (p-tert-butylphenyl) octyl phosphite, (4-fluorophenyl) octyl phosphite, (4-chlorophenyl) octyl phosphite, (4-bromophenyl) octyl phosphite, (4-trifluoromethylphenyl) octyl phosphite, (4-methoxyphenyl) octyl phosphite, (4-trifluoromethoxyphenyl) octyl phosphite, (4-nitrophenyl) octyl phosphite, (o-tolyl) octyl phosphite, (o-ethylphenyl) octyl phosphite, (o-isopropylphenyl) octyl phosphite, (o-tert-butylphenyl) octyl phosphite, (2-fluorophenyl) octyl phosphite Octyl (2-chlorophenyl) phosphite, Octyl (2-bromophenyl) phosphite, Octyl (2-trifluoromethylphenyl) phosphite, Octyl (2-methoxyphenyl) phosphite, Octyl (2-trifluoromethoxyphenyl) phosphite, Octyl (2-nitrophenyl) phosphite, Octyl (m-tolyl) phosphite, Octyl (m-ethylphenyl) phosphite, Octyl (m-isopropylphenyl) phosphite, Octyl (m-tert-butylphenyl) phosphite, Octyl (3-fluorophenyl) phosphite, Octyl (3-chlorophenyl) phosphite, Octyl (3-bromophenyl) phosphite, Octyl (3-trifluoromethylphenyl) phosphite, Octyl (3-methoxyphenyl) phosphite, Octyl (3-trifluoromethoxyphenyl) phosphite, Octyl (3-nitrophenyl) phosphite, Octyl naphthyl phosphite, Octyl (naphthyl) phosphiteOne or more of thienyl phosphite octyl ester, pyridyl phosphite octyl ester, and styryl phosphite octyl ester.

[0048] The catalytic system provided in this invention can be used for olefin copolymerization or polymerization, for example, it can catalyze the copolymerization (polymerization) reaction of isoprene and / or styrene.

[0049] This invention also provides a method for preparing an olefin block copolymer, comprising: subjecting isoprene and styrene to an olefin copolymerization reaction under the action of the above-mentioned catalytic system to obtain the olefin block copolymer.

[0050] Based on the aforementioned catalytic system, the above-mentioned method for preparing olefin block copolymers can yield olefin block copolymers with excellent self-healing capabilities. When this olefin block copolymer (self-healing polyolefin material) is damaged, it can quickly achieve self-repair by simply joining it at room temperature for a period of time. It can achieve surface bonding and overlapping without the need for external adhesives, resulting in high repair efficiency. Moreover, the repair process is simple and does not involve depolymerization. This olefin block copolymer exhibits good mechanical properties. In addition, the preparation method also has the advantages of readily available raw materials, low cost, and simple method.

[0051] In specific implementation, the temperature of the above-mentioned olefin copolymerization reaction can be -20~90℃, preferably 20~80℃; the pressure of the olefin copolymerization reaction can be 1-10 standard atmospheres, preferably 1-7 standard atmospheres; the time of the olefin copolymerization reaction can be 0.05~10h, preferably 0.5-2h.

[0052] Understandably, all the pressures mentioned above are gauge pressures. Furthermore, the olefin copolymerization system can be placed in a constant-temperature water bath to maintain a constant temperature.

[0053] The above olefin copolymerization reaction needs to be carried out in an inert atmosphere (such as nitrogen or high-purity nitrogen). In practice, the above olefin copolymerization reaction can be carried out in a polymerization flask that has been baked under vacuum and then filled with nitrogen.

[0054] The above-mentioned olefin copolymerization reaction is a solution polymerization. Therefore, in specific implementation, isoprene, styrene, and an organic solvent can be mixed and subjected to olefin copolymerization under the action of the above-mentioned catalytic system to prepare an olefin block copolymer. The above-mentioned organic solvent may include one or more of alkanes with 5 to 10 carbon atoms (C5-C10) and aromatic hydrocarbons with 6 to 8 carbon atoms (C6-C8), preferably one or more of heptane, n-hexane, cyclohexane, and toluene; in addition, the amount of the above-mentioned organic solvent can be limited according to the conventional amounts used in the art.

[0055] The isoprene and styrene mentioned above can be distilled in advance.

[0056] In some embodiments, the preparation method includes: mixing isoprene, styrene and an organic solvent, and then, under stirring, sequentially adding a main catalyst, an electron donor and an aluminum-containing co-catalyst to induce an olefin copolymerization reaction between isoprene and styrene. The olefin copolymerization reaction is then terminated by adding an ethanol solution comprising 2,6-di-tert-butyl-4-methylphenol and hydrochloric acid. The resulting polymer is precipitated with anhydrous ethanol, repeatedly washed, and then vacuum dried to constant weight to obtain the olefin block copolymer.

[0057] This invention also provides an olefin block copolymer, which is prepared according to the above method. This olefin block copolymer possesses excellent self-healing properties and good mechanical properties. When damage occurs to this olefin block copolymer (self-healing polyolefin material), it can quickly achieve self-repair by simply butturing at room temperature for a period of time. Surface bonding and overlapping can be achieved without the need for external adhesives, resulting in high repair efficiency. Furthermore, the repair process is simple and does not involve depolymerization.

[0058] The olefin block copolymer of this invention includes different amounts of crystalline hard segments and amorphous soft segments, wherein the crystalline hard segments include polystyrene segments and the amorphous soft segments include polyisoprene segments.

[0059] In some embodiments, the olefin block copolymer comprises 50% to 70% crystalline hard segments and 30% to 50% amorphous soft segments in molar percentage.

[0060] In some embodiments, the olefin block copolymer has a glass transition temperature of -30 to 0°C, a weight-average molecular weight of 125 to 670 kDa, a molecular weight distribution index of 2.0 to 2.5, a tensile strength of 6.0 to 22.0 MPa, and an elongation at break of 130% to 550%.

[0061] The present invention will be further described below through specific embodiments and comparative examples. Unless otherwise specified, the reagents, materials and instruments used below are all conventional reagents, materials and instruments, all of which are commercially available, and the reagents and materials involved can also be synthesized by conventional synthetic methods.

[0062] Different external electron donors were prepared according to the preparation methods provided in Preparation Examples 1 to 8.

[0063] Preparation Example 1

[0064] This preparation example provides a method for preparing an external electron donor, including:

[0065] 1) A raw material system was obtained by mixing phenylphosphoric acid (2.84 g, 20 mmol), pyridine (1.6 mL, 20 mmol) and 50 mL of dichloromethane;

[0066] 2) Dissolve phenyl chloroformate (3.13 g, 20 mmol) in 5 mL of dichloromethane to obtain a mixed solution containing phenyl chloroformate; add the mixed solution containing phenyl chloroformate dropwise to the above raw material system to obtain the reaction system;

[0067] 3) After heating the reaction system under reflux for 2 hours, cool it to room temperature, add 20 mL of 0.5 M hydrochloric acid aqueous solution, separate and collect the organic phase using a separatory funnel, dry it with anhydrous sodium sulfate, remove the solvent, and finally purify it using rapid column chromatography. The eluent may include a mixed solution of dichloromethane and ethyl acetate in a volume ratio of 5:1 to obtain a colorless oily substance (i.e., phenyl phenyl phosphite) (4.15 g, 95.0%). 1 H NMR (400 MHz, CDCl3) δ 7.40(t, 2H), 7.31(t, 2H), 7.26-7.21(m, 8H); 13 C (100 MHz, CDCl3) δ150.2, 135.0, 132.3, 128.8, 121.3, 120.3; 31 P NMR (162 MHz, CDCl3) δ 26.3.

[0068] Preparation Example 2

[0069] This preparation example is basically the same as Preparation Example 1, except that:

[0070] In step 1), phenylphosphoric acid (2.84 g, 20 mmol) was replaced with 4-methylphenylphosphoric acid (3.12 g, 20 mmol); other conditions remained unchanged.

[0071] The external electron donor obtained in Preparation Example 2 was a colorless oily substance (i.e., 4-methylphenylphosphite) (4.39 g, 94.5%). 1 H NMR (400 MHz, CDCl3) δ 7.40(t, 2H), 7.26-7.16(m, 7H), 2.37(s,3H); 13 C (100 MHz, CDCl3) δ 150.2, 141.4, 132.0,130.1,129.1, 121.3, 120.3, 21.3; 31 PNMR (162 MHz, CDCl3) δ 26.0.

[0072] Preparation Example 3

[0073] This preparation example is basically the same as Preparation Example 1, except that:

[0074] In step 1), phenylphosphoric acid (2.84 g, 20 mmol) was replaced with 4-fluorophenylphosphoric acid (3.20 g, 20 mmol); other conditions remained unchanged.

[0075] The external electron donor obtained in Preparation Example 3 was a colorless oily substance (i.e., phenyl 4-fluorophenyl phosphite) (4.41 g, 93.3%). 1 H NMR (400 MHz, CDCl3) δ 7.40(t, 2H), 7.26-7.16(m, 7H); 13 C (100 MHz, CDCl3) δ 150.2, 141.4, 132.0,130.1,129.1, 121.3, 120.3; 31 P NMR (162 MHz, CDCl3) δ 25.9.

[0076] Preparation Example 4

[0077] This preparation example is basically the same as Preparation Example 1, except that:

[0078] In step 1), phenylphosphoric acid (2.84 g, 20 mmol) was replaced with 4-chlorophenylphosphoric acid (3.53 g, 20 mmol); other conditions remained unchanged.

[0079] The external electron donor obtained in Preparation Example 4 was a colorless oily substance (i.e., phenyl 4-chlorophenylphosphite) (4.86 g, 96.2%). 1 H NMR (400 MHz, CDCl3) δ 7.40(t, 2H), 7.26-7.16(m, 7H); 13 C (100 MHz, CDCl3) δ 150.3, 141.2, 132.0,130.1,129.0, 121.3, 120.3; 31 P NMR (162 MHz, CDCl3) δ 26.1.

[0080] Preparation Example 5

[0081] This preparation example is basically the same as Preparation Example 1, except that:

[0082] In step 1), phenylphosphoric acid (2.84 g, 20 mmol) was replaced with 4-methoxyphenylphosphoric acid (3.44 g, 20 mmol); other conditions remained unchanged.

[0083] The external electron donor obtained in Preparation Example 5 was a colorless oily substance (i.e., phenyl 4-methoxyphenyl phosphite) (4.41 g, 93.3%).1 H NMR (400 MHz, CDCl3) δ 7.40(t, 2H), 7.26-7.20(m, 5H), 6.96(d,2H), 3.80(s, 3H); 13 C (100 MHz, CDCl3) δ 163.6, 150.2, 134.3, 133.3, 130.1,127.3, 121.3, 120.3, 56.0; 31 P NMR (162 MHz, CDCl3) δ 25.2.

[0084] Preparation Example 6

[0085] This preparation example is basically the same as Preparation Example 1, except that:

[0086] In step 1), phenylphosphine (2.84 g, 20 mmol) was replaced with naphthylphosphine (3.84 g, 20 mmol); other conditions remained unchanged.

[0087] The external electron donor obtained in Preparation Example 6 was a colorless oily substance (i.e., phenyl naphthyl phosphite) (4.83 g, 90.0%). 1 H NMR (400 MHz, CDCl3) δ 8.15(d, 2H), 8.12(d, 1H), 7.65 (t, 1H), 7.59 (t,1H), 7.52 (t, 1H), 7.40 (t, 2H), 7.21 (d, 3H); 13 C (100 MHz, CDCl3) δ 150.2,134.7, 134.5, 133.8, 131.3, 130.3, 130.1, 128.3, 126.3, 121.3, 120.3; 31 P NMR (162 MHz, CDCl3) δ 26.5.

[0088] Preparation Example 7

[0089] This preparation example is basically the same as Preparation Example 1, except that:

[0090] In step 1), phenylphosphine (2.84 g, 20 mmol) was replaced with thienylphosphine (2.96 g, 20 mmol); other conditions remained unchanged.

[0091] The external electron donor obtained in Preparation Example 7 was a colorless oily substance (i.e., phenyl thiophene phosphite) (4.13 g, 92.0%). 1H NMR (400 MHz, CDCl3) δ 7.75(s, 1H), 7.73(d, 1H), 7.40 (t, 2H), 7.21 (d,4H); 13 C (100 MHz, CDCl3) δ 150.2, 130.1, 127.4, 125.6, 121.3, 120.3; 31 P NMR (162 MHz, CDCl3) δ 26.2.

[0092] Preparation Example 8

[0093] This preparation example is basically the same as Preparation Example 1, except that:

[0094] In step 1), phenylphosphoric acid (2.84 g, 20 mmol) was replaced with pyridylphosphoric acid (2.86 g, 20 mmol); other conditions remained unchanged.

[0095] The external electron donor obtained in Preparation Example 8 was a colorless oily substance (i.e., phenyl pyridyl phosphite) (4.10 g, 93.5%). 1 H NMR (400 MHz, CDCl3) δ 8.42(d, 2H), 7.40 (d, 4H), 7.21 (t, 3H); 13 C (100MHz, CDCl3) δ 149.4, 142.2, 130.1, 124.7, 121.3, 120.3; 31 P NMR (162 MHz, CDCl3) δ 26.2.

[0096] Example 1

[0097] This embodiment provides a method for preparing polyisoprene, including:

[0098] In a nitrogen atmosphere, 5 mL of distilled isoprene monomer and 10 mL of toluene (solvent) were mixed. The temperature of the mixture was adjusted to 30 °C under stirring. Then, 10 μmol of Ti(OBu)4 complex, 50 μmol of phenyl phosphite (Preparation Example 1), and modified methylaluminoxane hexane solution (the amount of modified methylaluminoxane hexane solution added was determined according to an Al / Ti molar ratio of 1000) were added sequentially to allow the isoprene to undergo olefin polymerization for 6 h. Then, 1 mL of ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the olefin polymerization reaction. The resulting polymer was precipitated with anhydrous ethanol, washed repeatedly with anhydrous ethanol, and then dried under vacuum at 40 °C to constant weight to obtain polyisoprene.

[0099] Example 2

[0100] This embodiment provides a method for preparing an olefin block copolymer, comprising:

[0101] In a nitrogen atmosphere, 90 mmol of distilled isoprene monomer, 10 mmol of distilled styrene monomer, and 10 mL of toluene (solvent) were mixed. The temperature of the mixture was adjusted to 30 °C under stirring. Then, 10 μmol of Ti(OBu)4, 50 μmol of phenyl phosphite (Preparation Example 1), and a modified methylaluminoxane hexane solution (the amount of modified methylaluminoxane hexane solution added was determined according to an Al / Ti molar ratio of 1000) were added sequentially to allow isoprene and styrene to undergo an olefin copolymerization reaction for 6 h. Then, 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the olefin polymerization reaction. The resulting polymer was precipitated with anhydrous ethanol, washed repeatedly, and then dried under vacuum at 40 °C to constant weight to obtain an olefin block copolymer.

[0102] Example 3

[0103] This embodiment is basically the same as embodiment 2, except that:

[0104] The amount of distilled isoprene monomer was adjusted to 80 mmol, and the amount of distilled styrene monomer was adjusted to 20 mmol; other conditions remained unchanged.

[0105] Example 4

[0106] This embodiment is basically the same as embodiment 2, except that:

[0107] The amount of distilled isoprene monomer was adjusted to 70 mmol, and the amount of distilled styrene monomer was adjusted to 30 mmol; other conditions remained unchanged.

[0108] Example 5

[0109] This embodiment is basically the same as embodiment 2, except that:

[0110] The amount of distilled isoprene monomer was adjusted to 60 mmol, and the amount of distilled styrene monomer was adjusted to 40 mmol; other conditions remained unchanged.

[0111] Example 6

[0112] This embodiment is basically the same as embodiment 2, except that:

[0113] The amount of distilled isoprene monomer and the amount of distilled styrene monomer were adjusted to 50 mmol; other conditions remained unchanged.

[0114] Example 7

[0115] This embodiment is basically the same as embodiment 2, except that:

[0116] The amount of distilled isoprene monomer was adjusted to 40 mmol, and the amount of distilled styrene monomer was adjusted to 60 mmol; other conditions remained unchanged.

[0117] Example 8

[0118] This embodiment is basically the same as embodiment 2, except that:

[0119] The amount of distilled isoprene monomer was adjusted to 30 mmol, and the amount of distilled styrene monomer was adjusted to 70 mmol; other conditions remained unchanged.

[0120] Example 9

[0121] This embodiment is basically the same as embodiment 2, except that:

[0122] The amount of distilled isoprene monomer was adjusted to 20 mmol, and the amount of distilled styrene monomer was adjusted to 80 mmol; other conditions remained unchanged.

[0123] Example 10

[0124] This embodiment is basically the same as embodiment 2, except that:

[0125] The amount of distilled isoprene monomer was adjusted to 10 mmol, and the amount of distilled styrene monomer was adjusted to 90 mmol; other conditions remained unchanged.

[0126] Example 11

[0127] This embodiment is basically the same as embodiment 2, except that:

[0128] The amount of distilled isoprene monomer was adjusted to 0 mmol, and the amount of distilled styrene monomer was adjusted to 100 mmol; other conditions remained unchanged.

[0129] Example 12

[0130] This embodiment is basically the same as embodiment 11, except that:

[0131] The Ti(OBu)4 complex was replaced with a CpTiCl3 complex, where Cp includes a cyclopentadienyl group (C5H5); all other conditions remained unchanged.

[0132] Example 13

[0133] This embodiment is basically the same as embodiment 11, except that:

[0134] Replace the Ti(OBu)4 complex with the Ti(acac)3 complex, where acac is an acetylacetone group; keep all other conditions unchanged.

[0135] Example 14

[0136] This embodiment is basically the same as embodiment 9, except that:

[0137] Adjust the temperature of the mixing system to 50℃; keep other conditions unchanged.

[0138] Example 15

[0139] This embodiment is basically the same as embodiment 9, except that:

[0140] Adjust the temperature of the mixing system to 70℃; keep other conditions unchanged.

[0141] Example 16

[0142] This embodiment is basically the same as embodiment 9, except that:

[0143] Adjust the temperature of the mixing system to 90℃; keep other conditions unchanged.

[0144] Example 17

[0145] This embodiment is basically the same as embodiment 14, except that:

[0146] Adjust the amount of modified methylaluminoxane hexane solution added, specifically by determining the amount of the modified methylaluminoxane hexane solution added according to an Al / Ti molar ratio of 500; keep other conditions unchanged.

[0147] Example 18

[0148] This embodiment is basically the same as embodiment 14, except that:

[0149] Adjust the amount of modified methylaluminoxane hexane solution added, specifically by determining the amount of the modified methylaluminoxane hexane solution added according to an Al / Ti molar ratio of 1500; keep other conditions unchanged.

[0150] Example 19

[0151] This embodiment is basically the same as embodiment 17, except that:

[0152] The amount of phenyl phosphite (Preparation Example 1) was adjusted to 20 μmol; other conditions remained unchanged.

[0153] Example 20

[0154] This embodiment is basically the same as embodiment 17, except that:

[0155] The amount of phenyl phosphite (Preparation Example 1) was adjusted to 100 μmol; other conditions remained unchanged.

[0156] Example 21

[0157] This embodiment is basically the same as embodiment 17, except that:

[0158] The time for the olefin copolymerization reaction of isoprene and styrene was adjusted to 2 hours; other conditions remained unchanged.

[0159] Example 22

[0160] This embodiment is basically the same as embodiment 17, except that:

[0161] The time for the olefin copolymerization reaction of isoprene and styrene was adjusted to 12 hours; other conditions remained unchanged.

[0162] Example 23

[0163] This embodiment is basically the same as embodiment 17, except that:

[0164] 4-Methoxyphenylphosphite was used to replace phenylphosphite (Preparation Example 1); other conditions remained unchanged.

[0165] Example 24

[0166] This embodiment is basically the same as embodiment 17, except that:

[0167] 4-Methylphenylphosphite (Preparation Example 2) was used to replace phenylphosphite (Preparation Example 1); other conditions remained unchanged.

[0168] Example 25

[0169] This embodiment is basically the same as embodiment 17, except that:

[0170] 4-Fluorophenyl phosphite (Preparation Example 3) was used to replace phenyl phosphite (Preparation Example 1); other conditions remained unchanged.

[0171] Example 26

[0172] This embodiment is basically the same as embodiment 17, except that:

[0173] 4-Chlorophenyl phosphite (Preparation Example 4) was used to replace phenyl phosphite (Preparation Example 1); other conditions remained unchanged.

[0174] Example 27

[0175] This embodiment is basically the same as embodiment 17, except that:

[0176] Phenyl phosphite (Preparation Example 1) was replaced with naphthyl phosphite (Preparation Example 6); other conditions remained unchanged.

[0177] Example 28

[0178] This embodiment is basically the same as embodiment 17, except that:

[0179] The phenyl phosphite (Preparation Example 1) was replaced with thienyl phosphite (Preparation Example 7); other conditions remained unchanged.

[0180] Example 29

[0181] This embodiment is basically the same as embodiment 17, except that:

[0182] Phenyl phosphite (Preparation Example 1) was replaced with phenyl phosphite (Preparation Example 8); other conditions remained unchanged.

[0183] Example 30

[0184] This embodiment is basically the same as embodiment 11, except that:

[0185] Replace the Ti(OBu)4 complex with a CpTiMe3 complex, where Cp includes pentamethylcyclopentadiene (C5Me5) and Me is a methyl group; keep other conditions unchanged.

[0186] Example 31

[0187] This embodiment is basically the same as embodiment 11, except that:

[0188] Replace the Ti(OBu)4 complex with the TiY4 complex, where Y includes tert-butoxy (O-tert-Bu) and Me is methyl; keep other conditions unchanged.

[0189] Comparative Example 1

[0190] This comparative example is basically the same as Example 17, except that:

[0191] Without adding 50 μmol of phenyl phosphite (Preparation Example 1), other conditions remained unchanged.

[0192] Comparative Example 2

[0193] This comparative example is basically the same as Example 17, except that:

[0194] Phenyl phosphite was replaced with diphenyl phosphite (Preparation Example 1), while other conditions remained unchanged.

[0195] Experimental Example 1

[0196] The following parameters of the above embodiments and comparative examples were tested:

[0197] 1) The molar content (IP%) of the isoprene monomer corresponding structure and the molar content (St%) of the styrene monomer corresponding structure in polyisoprene were obtained from quantitative NMR spectra.

[0198] 2) Weight-average molecular weight (Mw) in polyisoprene: obtained by gel permeation chromatography (GPC).

[0199] 3) Molecular weight distribution index (PDI): Obtained by gel permeation chromatography (GPC).

[0200] 4) Glass transition temperature (Tg): Obtained by differential scanning calorimetry (DSC).

[0201] 5) Tensile strength: obtained by testing with a universal tensile strength testing machine;

[0202] 6) Elongation at break: obtained by testing with a universal tensile strength testing machine.

[0203] Test results

[0204] Table 1

[0205]

[0206] By comparing and analyzing the examples and comparative examples, it can be seen that by using the electron donor of the present invention, the amount of isoprene and styrene incorporated into the polymer (the molar content of the corresponding structure) can be effectively controlled. In addition, the polymer's number-average molecular weight, molecular weight distribution, glass transition temperature, tensile strength, elongation at break and other properties can meet the requirements.

[0207] Experimental Example 2

[0208] 1) Based on the quantitative NMR spectrum results, the molar percentage (%) of some sequence structures in polyisoprene in the following examples was further detected, and the detection results are shown in Table 2;

[0209] 2) The self-healing properties of polyisoprene in the following examples were tested: First, polyisoprene (the obtained polymer) was made into dumbbell-shaped strips with a size of 12*1*2mm. Its mechanical property A was tested. Then, its cross-section was completely cut and immediately joined together at 25°C. After standing for 5min, 30min, 60min, and 24h respectively, its mechanical property B was retested, and the self-healing efficiency was calculated. The self-healing efficiency = B / A*100%. The specific results are shown in Table 3.

[0210] Test results

[0211] Table 2. Molar percentage (%) of some sequence structures in polyisoprene

[0212]

[0213] Note: In Table 2, [SS] represents styrene-styrene structural unit, [II] represents isoprene-isoprene structural unit, [IS] represents isoprene-styrene structural unit, [SI] represents styrene-isoprene structural unit, nSt represents the sequence length of the polystyrene chain, and nIp represents the sequence length of the polyisoprene chain.

[0214] Table 3

[0215]

[0216] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A catalytic system for olefin copolymerization, characterized in that, The catalytic system includes a main catalyst, an aluminum-containing co-catalyst, and an electron donor; The structure of the electron donor is shown in Formula I: Equation I In Formula I, R is selected from substituted or unsubstituted C1-C6 alkyl, C1-C6 alkoxy, C3-C10 cycloalkyl, 3-10 membered heterocyclic, C3-10 cycloalkyloxy, C6-C20 aryl, or C6-C20 aryloxy groups. 1 R 2 R 3 R 4 R 5 Each is independently selected from hydrogen, halogen, substituted or unsubstituted C1-C6 alkyl, C1-C6 alkoxy, C3-C10 cycloalkyl, 3-10 heterocyclic, C3-C10 cycloalkyloxy, C6-C20 aryl or C6-C20 aryloxy, wherein the substituents of the substituted C1-C6 alkyl include C6-C20 aryl.

2. The catalytic system according to claim 1, characterized in that, The main catalyst is selected from CpMX3 or MY. n In this context, Cp is selected from cyclopentadienyl or pentamethylcyclopentadiene, X includes one or more of halogens and methyl groups, Y includes one or more of acetylacetonyl, tert-butoxy, and n-butoxy groups, n is 3 or 4, and M is a group IVB transition metal. And / or, the aluminum-containing cocatalyst includes one or more of alkylaluminum cocatalysts, alkylaluminum chloride cocatalysts, and alkoxyaluminum cocatalysts.

3. The catalytic system according to claim 1 or 2, characterized in that, The molar ratio of the electron donor to the main catalyst is (2~10):1; And / or, the molar ratio of the aluminum-containing co-catalyst to the main catalyst is (5~1500):1; And / or, M includes one or more of titanium, zirconium, and hafnium.

4. The catalytic system according to any one of claims 1-3, characterized in that, The electron donor is prepared by a method comprising at least the following processes: The compound represented by Formula II is added to a starting material system comprising substituted or unsubstituted arylphosphoric acid, a first organic solvent, and a second organic solvent, and the reaction system is carried out at 30–80°C to obtain the electron donor; wherein the compound represented by Formula II is shown below. Formula II In Formula II, X includes halogens; the substituents in the substituted aryl phosphates include R. 1 R 2 R 3 R 4 R 5 ; The first organic solvent includes one or more of cyclohexanoic acid, hexanoic acid, butyric acid, acrylic acid, benzoic acid, and pyridine, and the second organic solvent includes one or more of dichloromethane and acetone.

5. The catalytic system according to any one of claims 1-4, characterized in that, The electron donors include phenyl phosphite, (p-tolyl) phenyl phosphite, (p-ethylphenyl) phenyl phosphite, (p-isopropylphenyl) phenyl phosphite, (p-tert-butylphenyl) phenyl phosphite, (4-fluorophenyl) phenyl phosphite, (4-chlorophenyl) phenyl phosphite, (4-bromophenyl) phenyl phosphite, (4-trifluoromethylphenyl) phenyl phosphite, (4-methoxyphenyl) phenyl phosphite, (4-trifluoromethoxyphenyl) phenyl phosphite, (4-nitrophenyl) phenyl phosphite, (o-tolyl) phenyl phosphite, (o-ethylphenyl) phenyl phosphite, (o-isopropylphenyl) phenyl phosphite, (o-tert-butylphenyl) phenyl phosphite, (2-fluorophenyl) phenyl phosphite, (2-chlorophenyl) phenyl phosphite, ( 2-Bromophenyl)phosphite, (2-trifluoromethylphenyl)phosphite, (2-methoxyphenyl)phosphite, (2-trifluoromethoxyphenyl)phosphite, (2-nitrophenyl)phosphite, (m-tolyl)phosphite, (m-ethylphenyl)phosphite, (m-isopropylphenyl)phosphite, (m-tert-butylphenyl)phosphite, (3-fluorophenyl)phosphite, (3-chlorophenyl)phosphite, (3-bromophenyl)phosphite, (3-trifluoromethylphenyl)phosphite, (3-methoxyphenyl)phosphite, (3-trifluoromethoxyphenyl)phosphite, (3-nitrophenyl)phosphite, naphthylphosphite, thiopheneylphosphite, pyridylphosphite Phenyl phosphite, styryl phenyl phosphite, phenyl phosphite ethyl ester, (p-tolyl) phosphite ethyl ester, (p-ethylphenyl) phosphite ethyl ester, (p-isopropylphenyl) phosphite ethyl ester, (p-tert-butylphenyl) phosphite ethyl ester, (4-fluorophenyl) phosphite ethyl ester, (4-chlorophenyl) phosphite ethyl ester, (4-bromophenyl) phosphite ethyl ester, (4-trifluoromethylphenyl) phosphite ethyl ester, (4-methoxyphenyl) phosphite ethyl ester, (4-trifluoromethoxyphenyl) phosphite ethyl ester, (4-nitrophenyl) phosphite ethyl ester, (o-tolyl) phosphite ethyl ester, (o-ethylphenyl) phosphite ethyl ester, (o-isopropylphenyl) phosphite ethyl ester, (o-tert-butylphenyl) phosphite ethyl ester, (2-fluorophenyl) phosphite ethyl ester, (2-chlorophenyl) phosphite Ethyl phosphite, (2-bromophenyl) phosphite, (2-trifluoromethylphenyl) phosphite, (2-methoxyphenyl) phosphite, (2-trifluoromethoxyphenyl) phosphite, (2-nitrophenyl) phosphite, (m-tolyl) phosphite, (m-ethylphenyl) phosphite, (m-isopropylphenyl) phosphite, (m-tert-butylphenyl) phosphite, (3-fluorophenyl) phosphite, (3-chlorophenyl) phosphite, (3-bromophenyl) phosphite, (3-trifluoromethylphenyl) phosphite, (3-methoxyphenyl) phosphite, (3-trifluoromethoxyphenyl) phosphite, (3-nitrophenyl) phosphite, naphthyl phosphite, thiophene phosphite.Ethyl pyridyl phosphite, ethyl styryl phosphite, butyl phenyl phosphite, butyl (p-tolyl) phosphite, butyl (p-ethylphenyl) phosphite, butyl (p-isopropylphenyl) phosphite, butyl (p-tert-butylphenyl) phosphite, butyl (4-fluorophenyl) phosphite, butyl (4-chlorophenyl) phosphite, butyl (4-bromophenyl) phosphite, butyl (4-trifluoromethylphenyl) phosphite, butyl (4-methoxyphenyl) phosphite, butyl (4-trifluoromethoxyphenyl) phosphite, butyl (4-nitrophenyl) phosphite, butyl (o-tolyl) phosphite, butyl (o-ethylphenyl) phosphite, butyl (o-isopropylphenyl) phosphite, butyl (o-tert-butylphenyl) phosphite, butyl (2-fluorophenyl) phosphite, butyl (2-chlorophenyl) phosphite... (Phenyl) phosphite butyl ester, (2-bromophenyl) phosphite butyl ester, (2-trifluoromethylphenyl) phosphite butyl ester, (2-methoxyphenyl) phosphite butyl ester, (2-trifluoromethoxyphenyl) phosphite butyl ester, (2-nitrophenyl) phosphite butyl ester, (m-tolyl) phosphite butyl ester, (m-ethylphenyl) phosphite butyl ester, (m-isopropylphenyl) phosphite butyl ester, (m-tert-butylphenyl) phosphite butyl ester, (3-fluorophenyl) phosphite butyl ester, (3-chlorophenyl) phosphite butyl ester, (3-bromophenyl) phosphite butyl ester, (3-trifluoromethylphenyl) phosphite butyl ester, (3-methoxyphenyl) phosphite butyl ester, (3-trifluoromethoxyphenyl) phosphite butyl ester, (3-nitrophenyl) phosphite butyl ester, naphthyl phosphite butyl ester, thiophene Butyl phosphate, pyridyl phosphite, styryl phosphite, phenyl octyl phosphite, (p-tolyl) octyl phosphite, (p-ethylphenyl) octyl phosphite, (p-isopropylphenyl) octyl phosphite, (p-tert-butylphenyl) octyl phosphite, (4-fluorophenyl) octyl phosphite, (4-chlorophenyl) octyl phosphite, (4-bromophenyl) octyl phosphite, (4-trifluoromethylphenyl) octyl phosphite, (4-methoxyphenyl) octyl phosphite, (4-trifluoromethoxyphenyl) octyl phosphite, (4-nitrophenyl) octyl phosphite, (o-tolyl) octyl phosphite, (o-ethylphenyl) octyl phosphite, (o-isopropylphenyl) octyl phosphite, (o-tert-butylphenyl) octyl phosphite, (2-fluorophenyl) octyl phosphite Octyl (2-chlorophenyl) phosphite, Octyl (2-bromophenyl) phosphite, Octyl (2-trifluoromethylphenyl) phosphite, Octyl (2-methoxyphenyl) phosphite, Octyl (2-trifluoromethoxyphenyl) phosphite, Octyl (2-nitrophenyl) phosphite, Octyl (m-tolyl) phosphite, Octyl (m-ethylphenyl) phosphite, Octyl (m-isopropylphenyl) phosphite, Octyl (m-tert-butylphenyl) phosphite, Octyl (3-fluorophenyl) phosphite, Octyl (3-chlorophenyl) phosphite, Octyl (3-bromophenyl) phosphite, Octyl (3-trifluoromethylphenyl) phosphite, Octyl (3-methoxyphenyl) phosphite, Octyl (3-trifluoromethoxyphenyl) phosphite, Octyl (3-nitrophenyl) phosphite, Octyl naphthyl phosphite, Octyl (naphthyl) phosphiteOne or more of thienyl phosphite octyl ester, pyridyl phosphite octyl ester, and styryl phosphite octyl ester.

6. A method for preparing an olefin block copolymer, characterized in that, include: The olefin block copolymer is prepared by subjecting isoprene and styrene to an olefin copolymerization reaction under the action of the catalytic system described in any one of claims 1-5.

7. The preparation method according to claim 6, characterized in that, The temperature for the olefin copolymerization reaction is -20 to 90°C, preferably 20 to 80°C; And / or, the pressure of the olefin copolymerization reaction is 1-10 standard atmospheres, preferably 1-7 standard atmospheres; And / or, the copolymerization time of the olefin is 0.05~10h, preferably 0.5-2h; And / or, the molar ratio of isoprene to styrene is 0.3 to 0.

7.

8. An olefin block copolymer, characterized in that, The olefin block copolymer is obtained according to the preparation method described in claim 6 or 7.

9. The olefin block copolymer according to claim 8, characterized in that, The olefin block copolymer comprises 50% to 70% crystalline hard segments and 30% to 50% amorphous soft segments in molar percentage, wherein the crystalline hard segments include polystyrene segments and the amorphous soft segments include polyisoprene segments.

10. The olefin block copolymer according to claim 8 or 9, characterized in that, The olefin block copolymer has a glass transition temperature of -30 to 0°C, a weight-average molecular weight of 125 to 670 kDa, a molecular weight distribution index of 2.0 to 2.5, a tensile strength of 6.0 to 22.0 MPa, and an elongation at break of 130% to 550%.

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