Preparation method of ultrahigh-toughness 4-methyl-1-pentene / alpha-olefin copolymer

Abstract

The invention discloses a preparation method of a 4-methyl-1-pentene / alpha-olefin copolymer with ultrahigh toughness. The method comprises the following steps: 1) fully mixing a catalyst system, a solvent and a small amount of 4-methyl-1-pentene for a period of time to prepare a prepolymerization solution; 2) feeding 4-methyl-1-pentene and alpha-olefin into a reactor according to a constant ratio point, then adding the prepolymerization liquid, a solvent and an optional molecular weight regulator into the reactor, and reacting for a period of time to obtain a polymerization liquid; and (3) quenching the polymerization liquid through a quenching agent to obtain the 4-methyl-1-pentene / alpha-olefin copolymer.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of olefin copolymer, and particularly relates to a preparation method of 4-methyl-1-pentene / alpha-olefin copolymer with ultrahigh toughness. BACKGROUND

[0002] Poly-4-methyl-1-pentene (PMP) is a thermoplastic resin with high transparency, low density, high crystallinity, high heat resistance and excellent dielectric properties, and is widely used in medical devices, high-frequency electronic devices and separation membranes, etc. However, the toughness of PMP is poor, which is manifested as low elongation at break and insufficient impact strength, thereby limiting its application in flexible products (such as films, hollow fiber membranes, etc.). In order to improve the toughness of PMP, the prior art usually adopts copolymerization modification of 4-methyl-1-pentene and alpha-olefin (such as 1-hexene, 1-octene), for example, CN101056895A and CN102089379A both mention that the copolymerization of alpha-olefin can adjust the flexibility and mechanical properties of PMP.

[0003] In addition to toughness, strength and release property are also key parameters of 4-methyl-1-pentene / alpha-olefin copolymer film in processing. Among them, toughness ensures that the film is not easy to break in the processing process (such as extrusion, stretching), improves the production stability and yield, and in the use link, makes the film more resistant to folding, puncture and accidental tearing, thereby prolonging the service life in the application of high-temperature preservative film, medical device packaging, etc. The strength endows the film with excellent dimensional stability and creep resistance, so that it is not easy to deform under mechanical stress, so that it can provide stable mechanical support when used as a release film or a bearing film in the pressing process of electronic components (such as flexible circuit board FPC), preventing the deformation or damage of the circuit in the high-temperature and high-pressure pressing process. The release property refers to the property that the film has no or slight adhesion after being closely attached to a specific material, and can be quickly peeled off from the specific material under the action of a small peeling force, and there is no residue and no pollution after peeling.

[0004] However, in general, the strength / release property and the content of structural units derived from alpha-olefin are negatively correlated, and the toughness and the content of structural units derived from alpha-olefin are positively correlated, so it is difficult for the existing copolymerization scheme to simultaneously consider the strength / release property and the toughness of the copolymer, therefore, how to prepare 4-methyl-1-pentene / alpha-olefin copolymer with good strength / release property and toughness has become the research and development direction of the technical personnel in the field. SUMMARY

[0005] In order to solve the above technical problems, the application provides a preparation method of 4-methyl-1-pentene / alpha-olefin copolymer with ultrahigh toughness.

[0006] To achieve the above object, the technical scheme adopted by the application is as follows:

[0007] A method for preparing a super-tough 4-methyl-1-pentene / alpha-olefin copolymer, comprising the following steps:

[0008] 1) mixing a catalyst system, a solvent and a small amount of 4-methyl-1-pentene for a period of time to prepare a prepolymerization liquid; this step can expose more Z-N catalyst active sites, improve catalytic activity, and improve the morphology of the polymer.

[0009] 2) feeding 4-methyl-1-pentene and alpha-olefin to the reactor according to the constant ratio point, then adding the above prepolymerization liquid, solvent and optional molecular weight regulator to the reactor, and reacting for a period of time to obtain a polymerization liquid;

[0010] 3) quenching the above polymerization liquid with a quenching agent to obtain a 4-methyl-1-pentene / alpha-olefin copolymer;

[0011] The catalyst system comprises a main catalyst, a cocatalyst and an external electron donor.

[0012] Unless otherwise specified, the above reaction steps are carried out under a protective atmosphere and under anaerobic and anhydrous conditions.

[0013] The composition of the polymer at the constant ratio point is the same as that of the monomer, and by controlling the monomer ratio according to the constant ratio point, the structure of the copolymer can be precisely controlled. In the preparation of the 4-methyl-1-pentene / alpha-olefin copolymer, the constant ratio point feeding realizes a significant improvement in material toughness, solving the technical problem that the strength / demolding property and toughness of the copolymer are difficult to balance.

[0014] The relationship between the constant ratio point feeding amount and the monomer reactivity ratio is as follows:

[0015]

[0016] Wherein, F1 is the molar content of the structural unit of 4-methyl-1-pentene in the copolymer at the constant ratio point, in %;

[0017] f1 is the molar content of 4-methyl-1-pentene in the monomer composition at the constant ratio point, in %;

[0018] r1 is the reactivity ratio of 4-methyl-1-pentene;

[0019] r2 is the reactivity ratio of alpha-olefin;

[0020] r1>1, and r2>1.

[0021] In some embodiments, the main catalyst is a Ziegler-Natta catalyst;

[0022] Preferably, the co-catalyst is one or more of triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-pentylaluminum, triisopentylaluminum, methyldiethylaluminum, methyldi-n-propylaluminum, methyldiisopropylaluminum, methyldi-n-butylaluminum, methyldiisobutylaluminum, diethyl-n-propylaluminum, diethylisopropylaluminum, diethyl-n-butylaluminum, diethylisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, propylaluminoxane, isobutylaluminoxane, diisobutylaluminoxane;

[0023] Preferably, the external electron donor is one or more of trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, triethylmethoxysilane, diethyl dimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyl dimethoxysilane, diisopropyl dimethoxysilane, phenyltriethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxysilane, isopropyl tert-butyl dimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, methyldicyclopentylmethoxysilane, ethylcyclohexyldimethoxysilane, triisopropylmethoxysilane, tert-butyltriethoxysilane, diphenyldiethoxysilane, cycloheptyldimethoxysilane, methylphenyldiethoxysilane, diisopropyl diethoxysilane, cyclohexylisopropyl dimethoxysilane, triphenylmethoxysilane, isobutylmethyldimethoxysilane, and n-butyltriethoxysilane.

[0024] In some embodiments, the molar ratio of the procatalyst, external electron donor, and co-catalyst is 1: (10-20): (100-200).

[0025] In some embodiments, in step 1), the feeding amount of 4-methyl-1-pentene is 160-8000 times the molar amount of the procatalyst.

[0026] In some embodiments, in step 2), the feeding amount of 4-methyl-1-pentene is 0.5x10 5 -20x10 5 times the molar amount of the procatalyst.

[0027] In some embodiments, preferably, the molecular weight regulator is hydrogen;

[0028] Preferably, in step 2), the addition of the molecular weight regulator controls the system pressure to be 20-60 kPaG.

[0029] In some embodiments, the solvent is an alkane solvent, preferably one or more of n-hexane, n-heptane, n-decane.

[0030] In some implementations, the reaction temperature in step 1) is 10-35°C and the reaction time is 5-180 min;

[0031] Preferably, the reaction temperature in step 2) is 30-60℃ and the reaction time is 3-15h.

[0032] In some embodiments, the quenching agent is selected from one or more of water, ethanol, propanol, butanol, octanol, and isooctanol.

[0033] In some embodiments, the α-olefin is selected from C6-20 olefins, preferably one or more of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetracene, 1-tetradecene, 1-pentadecanene, 1-hexadecene, 1-heptadecene, 1-heptadecene, 1-octadecene, 1-nonadecanene, and 1-eicosene.

[0034] This invention involves feeding 4-methyl-1-pentene and α-olefin at a constant ratio point, resulting in a copolymer that not only possesses high strength and excellent release properties but also exhibits ultra-high toughness. Universal tensile testing shows that the elongation at break of the 4-methyl-1-pentene / α-olefin copolymer is 200-500%, and the impact strength is 50-100 kJ / m. 2 The toughness has been improved by more than 5 times. Detailed Implementation

[0035] The present invention will be further illustrated below with specific embodiments. These embodiments are merely illustrative and do not limit the scope of the invention.

[0036] Unless otherwise specified, the raw materials and reagents used in the following embodiments of the present invention can be obtained commercially available; wherein,

[0037] 4-Methyl-1-pentene, Tokyo Chemical Industry Co., Ltd. (TCI), purity >98%;

[0038] 1-Pentene, Beijing Innocare Technology Co., Ltd., purity >99%;

[0039] 1-Hexene, Beijing Innocare Technology Co., Ltd., purity >99%;

[0040] 1-Eicosene, Beijing Innocare Technology Co., Ltd., purity >99%;

[0041] Trimethylmethoxysilane, Beijing Innocare Technology Co., Ltd., purity >99%;

[0042] Methyltrimethoxysilane, Beijing Innocare Technology Co., Ltd., purity >99%;

[0043] 1 mol / L triethylaluminum in n-heptane, 1 mol / L triisobutylaluminum in n-hexane, 1 mol / L methylaluminoxane in n-hexane, 1 mol / L diethylaluminum chloride in n-hexane, 1 mol / L modified methylaluminoxane in n-hexane, 1 mol / L tri-n-butylaluminum in n-hexane, 1 mol / L ethylaluminum dichloride in n-hexane, 1 mol / L tri-n-pentylaluminum in n-hexane, 1 mol / L isobutylaluminoxane in n-hexane, 1 mol / L diisobutylaluminoxane in n-hexane, 1 mol / L methyldiethylaluminum in n-hexane, 1 mol / L diethyl-n-propylaluminum in n-hexane, 1 mol / L triisopropylaluminum in n-hexane, 1 mol / L triisopentylaluminum in n-hexane, 1 mol / L methyldi-n-butylaluminum in n-hexane, all from Shanghai Aladdin Biochem Technology Co., Ltd.

[0044] Hydrogen, Yantai Minggu New Energy Co., Ltd., purity 99.999%.

[0045] The molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the polymers obtained in the examples and comparative examples were determined by GPC-IR. w The analysis was performed by GPC-IR instrument, which was built-in three MIXED chromatographic columns in series, size 300*7.5 mm; equipped with infrared, viscosity, laser three kinds of detectors, commonly used IR5 MCT polyolefin special infrared detector for detection; the sample was automatically injected 8 ml of trichlorobenzene solvent in the high temperature zone (160°C) of the instrument automatic sampler, shaken and dissolved for one hour, then 200 μL was extracted for testing, the infrared detector temperature was 150°C, and the molecular weight standard was PS, and the monomer standard line was established by a series of different monomer content gradients of PMP.

[0046] The composition content of 4-methyl-1-pentene / α-olefin copolymer was determined by high temperature gel permeation chromatography (GPC) with an infrared detector (GPC-IR). 13 C NMR (Germany Bruker 600M) was analyzed with deuterated dichlorobenzene as the solvent, the polymer was dissolved in a 10 mm sample nuclear magnetic tube, and the test temperature was 120°C, and the carbon spectrum was scanned more than 5000 times.

[0047] The sample preparation method of the polymers obtained in the examples and comparative examples was as follows: the polymer raw material was placed in a flat vulcanizing machine, and hot pressing treatment was carried out at 290°C and 5 MPa pressure to prepare a film with a length of 70 mm, a width of 30 mm and a thickness of 100 μm or a sheet with a length of 80 mm, a width of 10 mm and a thickness of 4 mm, and the film / sheet was naturally cooled to room temperature and then used for subsequent performance tests such as tensile strength, bending strength, elongation at break, impact strength, surface tension and dyne value.

[0048] ​The elongation at break of the polymers obtained in the Examples and Comparative Examples was determined according to the ASTM D638 standard. Specifically, using a universal tensile machine, a film was made into a 1B dumbbell-shaped test specimen as specified in the ISO 527-2 standard. The initial gauge length between the clamps was 25 mm. The test was performed after environmental conditioning at a temperature of 3 ± 2 °C and a relative humidity of 50 ± 10% for at least 4 hours. The test was performed at a tensile speed of 50 mm / min until the specimen broke. The elongation at break was calculated by the system automatically recorded by the universal tensile machine or by the following formula:

[0049] Elongation at break (%) = [(gauge length at break - original gauge length) / original gauge length] x 100%

[0050] The tensile strength of the polymers obtained in the Examples and Comparative Examples was determined according to the ASTM D638 standard, making a film into a standard dumbbell-shaped test specimen (1B type as specified in the ISO 527-2). On a universal tensile machine, the test specimen was stretched at a constant speed (50 mm / min) until it broke. The test environment temperature was preferably 23 ± 2 °C and the relative humidity was 50 ± 10%.

[0051] Tensile strength (MPa) = maximum tensile force sustained by the test specimen before it broke / (width of the narrow portion of the test specimen x thickness of the narrow portion of the test specimen)

[0052] The flexural strength (resistance to bending) of the polymers obtained in the Examples and Comparative Examples was determined according to the ASTM D790 standard, using the three-point bending method. A long strip-shaped sheet of a specified size (80 mm x 10 mm x 4 mm) was placed horizontally on two support rollers. A load was applied to the test specimen by a press head located in the middle of the two support points at a constant displacement rate (1.3 mm / min) until the test specimen broke or reached a specified deflection.

[0053] Flexural strength (MPa) = (3 x maximum load recorded at the time of breakage of the test specimen x span between the support rollers) / (2 x width of the test specimen x thickness of the test specimen)

[0054] The unnotched impact strength of the polymers obtained in the Examples and Comparative Examples was determined according to the ISO 179-1 standard, using a “unnotched” test specimen. Specifically, a cuboid-shaped sheet of a standard size (80 mm x 10 mm x 4 mm) was supported horizontally on two support points of a simply supported beam impact testing machine. A single high-speed impact was performed using a pendulum at the center of the span of the test specimen. The test result was expressed as the energy absorbed at the time of breakage of the test specimen and was calculated as the impact strength per unit cross-sectional area of the test specimen (unit: kJ / m 2 ).

[0055] The dyne value (unit: mN / m) of the polymer obtained in the examples and comparative examples is determined according to the dyne pen test method: after the surface of the polymer film is smoothed and cleaned, a 20-40 mN / m series gradient dyne pen is used to draw a straight line with a length of 5-10 mm on the surface of the film in turn, and if the liquid film does not shrink and break within 2 seconds, the corresponding dyne value is obtained, which directly reflects the surface tension and release property of the polymer.

[0056] In the present application, the reactivity ratio r1 of 4-methyl-1-pentene and the reactivity ratio r2 of the α-olefin are calculated by the following method:

[0057] Monomer feeding ratio:

[0058] Copolymer composition ratio:

[0059] Wherein, [M1] is the molar mass of 4-methyl-1-pentene monomer, [M2] is the molar mass of α-olefin monomer, m1 is the content of 4-methyl-1-pentene structural unit, m2 is the content of α-olefin structural unit, A is the feeding ratio (molar ratio) of 4-methyl-1-pentene / α-olefin monomers in the copolymerization reaction, a is the copolymerization reactivity ratio of 4-methyl-1-pentene / α-olefin monomers, and r1 is the copolymerization reactivity ratio of 4-methyl-1-pentene. 13 The ratio of the content of 4-methyl-1-pentene structural unit to the content of α-olefin structural unit in the copolymer calculated by C NMR.

[0060] Substitute A and a into the copolymerization equation of 4-methyl-1-pentene / α-olefin:

[0061]

[0062] That is,

[0063] Multiply both sides of formula (1-5) by (A+r2) and expand to get:

[0064] aA+ar2=r1A 2 +A (1-6)

[0065] Move A to the left side and ar2 to the right side of formula (1-6) to get:

[0066] A(α-1)=r1A 2 -ar2 (1-7)

[0067] Divide both sides of formula (1-7) by a to get:

[0068]

[0069] Let Y equal X equals The experimental data (A, a) of copolymerization reaction of 4-methyl-1-pentene and α-olefin at a certain temperature is converted into (Y, X), 6 data points (X, Y) are taken, and a linear equation Y = r1·X-r2 is fitted to obtain the reactivity ratio r1 of 4-methyl-1-pentene and the reactivity ratio r2 of α-olefin at this time.

[0070] Example 1

[0071] A preparation method of a super-high-toughness 4-methyl-1-pentene / α-olefin copolymer, comprising the following steps:

[0072] 1) Under the conditions of a protective atmosphere and no oxygen and water, a small amount of 4-methyl-1-pentene (0.8 mmol), Z-N catalyst (5 μmol), trimethylmethoxysilane (50 μmol), 1 mol / L triethylaluminum n-heptane solution (0.5 mmol), and 5 mL of n-heptane solvent are first subjected to a prepolymerization reaction, and are fully mixed at 10°C for 5 min to prepare a prepolymerization solution;

[0073] 2) Under the conditions of a protective atmosphere and no oxygen and water, 4-methyl-1-pentene (790 mmol) and 1-hexene (15.8 mmol) are first fed according to a constant ratio point, and then the prepolymerization solution of step 1), hydrogen (60 kPaG), and n-heptane solvent (200 mL) are added to a reactor and reacted at 30°C for 15 h to obtain a polymerization solution;

[0074] 3) The polymerization solution is quenched by ethanol as a quenching agent to obtain a 4-methyl-1-pentene / α-olefin copolymer.

[0075] In this example, it can be known from the GPC-IR instrument that M w 、 It can be known that M w 、 The monomer reactivity ratio r1 of 4-methyl-1-pentene is 1.04, the monomer reactivity ratio r2 of 1-hexene is 3.10, r1>1, r2>1, the binary copolymerization reaction has a constant ratio point, and the constant ratio point is 0.98. The high-temperature 13 C NMR can know that the content of 4-methyl-1-pentene unit in the 4-methyl-1-pentene / 1-hexene copolymer is 0.98, which indicates that the constant ratio point polymerization is achieved.

[0076] Example 2

[0077] A preparation method of a super-high-toughness 4-methyl-1-pentene / α-olefin copolymer, comprising the following steps:

[0078] 1) Under a protective atmosphere and under oxygen-free and anhydrous conditions, a small amount of 4-methyl-1-pentene (8 mmol), Zn catalyst (1 μmol), dimethyldimethoxysilane (20 μmol), 1 mol / L triisobutylaluminum in n-hexane solution (0.2 mmol) and 5 mL of n-heptane solvent were first subjected to a prepolymerization reaction. The mixture was thoroughly mixed at 35 °C for 30 min to prepare a prepolymerized solution.

[0079] 2) Under a protective atmosphere and under oxygen-free and anhydrous conditions, 4-methyl-1-pentene (790 mmol) and 1-heptene (59.5 mmol) were first fed at a constant ratio point. Then, the prepolymer solution from step 1), hydrogen (40 kPaG) and n-heptane solvent (200 mL) were added to the reactor at 60 °C and reacted for 3 h to obtain the polymer solution.

[0080] 3) Quench the above polymer solution with propanol as a quencher to obtain a 4-methyl-1-pentene / α-olefin copolymer.

[0081] In this embodiment, M can be determined using a GPC-IR instrument. w , It can be known that M w , The monomer reactivity ratios (r1) for 4-methyl-1-pentene are 150,000 and 6.54, respectively, and the monomer reactivity ratio (r2) for 1-heptene is 4.80. Since r1 > 1 and r2 > 1, the binary copolymerization reaction exhibits a constant ratio point of 0.93. (High temperature) 13 C NMR analysis revealed that the 4-methyl-1-pentene unit content in the 4-methyl-1-pentene / 1-heptene copolymer was 0.93, indicating that constant-point polymerization was achieved.

[0082]

Example 3

[0083] A method for preparing an ultra-high toughness 4-methyl-1-pentene / α-olefin copolymer includes the following steps:

[0084] 1) Under a protective atmosphere and under oxygen-free and anhydrous conditions, a small amount of 4-methyl-1-pentene (3 mmol), Zn catalyst (3 μmol), trimethylmethoxysilane (45 μmol), a 1 mol / L hexane solution of methylaluminoxane (0.45 mmol), and 5 mL of heptane solvent were subjected to a prepolymerization reaction. The mixture was thoroughly mixed at 20 °C for 30 min to prepare a prepolymerized liquid.

[0085] 2) Under the conditions of protective atmosphere and anaerobic and anhydrous, first, 4-methyl-1-pentene (790 mmol) and 1-octene (87.78 mmol) are fed according to the constant ratio point, then the prepolymerization solution of step 1), hydrogen (32 kPaG) and n-heptane solvent (200 mL) are added into the reactor under the condition of 40℃ for 8h to obtain a polymerization solution;

[0086] 3) The above polymerization solution is quenched by butanol as a quenching agent to obtain a 4-methyl-1-pentene / α-olefin copolymer.

[0087] In this embodiment, it can be known from the GPC-IR instrument that M w 、 It can be known that M w 、 The monomer reactivity ratio r1 of 4-methyl-1-pentene is 1.32, the monomer reactivity ratio r2 of 1-octene is 3.70, r1>1, r2>1, the binary copolymerization reaction has a constant ratio point, and the constant ratio point is 0.90. The high-temperature 13 C NMR can know that the content of 4-methyl-1-pentene unit in the 4-methyl-1-pentene / 1-octene copolymer is 0.90, which indicates that the constant ratio point polymerization is realized.

[0088]

Embodiment 4

[0089] A preparation method of a super-high-toughness 4-methyl-1-pentene / α-olefin copolymer, comprising the following steps:

[0090] 1) Under the conditions of protective atmosphere and anaerobic and anhydrous, a small amount of 4-methyl-1-pentene (6 mmol), Z-N catalyst (2 μmol), cyclohexylmethyldimethoxysilane (36 μmol), 1 mol / L diethylaluminum chloride n-hexane solution (0.36 mmol) and 5 mL n-heptane solvent are first subjected to prepolymerization, and are fully mixed under the condition of 25℃ for 60 min to prepare a prepolymerization solution;

[0091] 2) Under the conditions of protective atmosphere and anaerobic and anhydrous, first, 4-methyl-1-pentene (790 mmol) and 1-nonene (140 mmol) are fed according to the constant ratio point, then the prepolymerization solution of step 1), hydrogen (26 kPaG) and n-heptane solvent (200 mL) are added into the reactor under the condition of 45℃ for 10h to obtain a polymerization solution;

[0092] 3) The above polymerization solution is quenched by octanol as a quenching agent to obtain a 4-methyl-1-pentene / α-olefin copolymer.

[0093] In this embodiment, it can be known from the GPC-IR instrument that M w 、 It can be known that Mw , 230000 and 6.25, respectively, the monomer reactivity ratio r1 of 4-methyl-1-pentene is 1.44, the monomer reactivity ratio r2 of 1-nonene is 3.27, r1>1, r2>1, the binary copolymerization reaction has a constant ratio point, and the constant ratio point is 0.85. High temperature 13 C NMR shows that the content of 4-methyl-1-pentene units in the 4-methyl-1-pentene / 1-nonene copolymer is 0.85, indicating that the constant ratio point polymerization is achieved.

[0094]

Example 5

[0095] A method for preparing a 4-methyl-1-pentene / α-olefin copolymer with ultrahigh toughness, comprising the following steps:

[0096] 1) Under the conditions of a protective atmosphere and no oxygen and water, a small amount of 4-methyl-1-pentene (10 mmol), Z-N catalyst (1.25 μmol), dicyclopentyl dimethoxysilane (20 μmol), 1 mol / L modified methylaluminoxane n-n-hexane solution (0.2 mmol), and 5 mL of n-heptane solvent are first subjected to a prepolymerization reaction, and are fully mixed at 30°C for 120 min to prepare a prepolymerization liquid;

[0097] 2) Under the conditions of a protective atmosphere and no oxygen and water, 4-methyl-1-pentene (790 mmol) and 1-decene (197.5 mmol) are first fed according to the constant ratio point, and then the prepolymerization liquid of step 1), hydrogen (21 kPaG), and n-heptane solvent (200 mL) are added to the reactor and reacted at 50°C for 12 h to obtain a polymerization liquid;

[0098] 3) The polymerization liquid is quenched by using isooctanol as a quenching agent to obtain a 4-methyl-1-pentene / α-olefin copolymer.

[0099] In this example, it can be known from the GPC-IR instrument that M w , It can be known that M w , 280000 and 9.21, respectively, the monomer reactivity ratio r1 of 4-methyl-1-pentene is 1.52, the monomer reactivity ratio r2 of 1-decene is 3.02, r1>1, r2>1, the binary copolymerization reaction has a constant ratio point, and the constant ratio point is 0.80. High temperature 13 C NMR shows that the content of 4-methyl-1-pentene units in the 4-methyl-1-pentene / 1-decene copolymer is 0.80, indicating that the constant ratio point polymerization is achieved.

[0100]

Example 6

[0101] A preparation method of a super-high toughness 4-methyl-1-pentene / alpha-olefin copolymer, comprising the following steps:

[0102] 1) Under a protective atmosphere and anaerobic and anhydrous conditions, a small amount of 4-methyl-1-pentene (1.6 mmol), Z-N catalyst (15.8 μmol), diisopropyl dimethoxysilane (180 μmol), 1 mol / L tri-n-butyl aluminum n-hexane solution (1.1 mmol) and 5 mL of n-heptane solvent are first subjected to a prepolymerization reaction, and are fully mixed at 15 ℃ for 45 min to prepare a prepolymerization liquid;

[0103] 2) Under a protective atmosphere and anaerobic and anhydrous conditions, 4-methyl-1-pentene (790 mmol) and 1-undecene (263.33 mmol) are first fed according to a constant ratio point, and then the prepolymerization liquid of step 1), hydrogen (20 kPaG) and n-heptane solvent (200 mL) are added to a reactor and reacted at 35 ℃ for 4 h to obtain a polymerization liquid;

[0104] 3) The polymerization liquid is quenched by water as a quenching agent to obtain a 4-methyl-1-pentene / alpha-olefin copolymer.

[0105] In this embodiment, it can be known from the GPC-IR instrument that M w 、 It can be known that M w 、 The monomer reactivity ratio r1 of 4-methyl-1-pentene is 1.64, the monomer reactivity ratio r2 of 1-undecene is 2.80, r1>1, r2>1, the binary copolymerization reaction has a constant ratio point, and the constant ratio point is 0.75. High temperature 13 The C NMR can know that the content of 4-methyl-1-pentene units in the 4-methyl-1-pentene / 1-undecene copolymer is 0.75, which indicates that the constant ratio point polymerization is achieved.

[0106]

Example 7

[0107] A preparation method of a super-high toughness 4-methyl-1-pentene / alpha-olefin copolymer, comprising the following steps:

[0108] 1) Under a protective atmosphere and anaerobic and anhydrous conditions, a small amount of 4-methyl-1-pentene (4 mmol), Z-N catalyst (4 μmol), phenyl triethoxysilane (52 μmol), 1 mol / L ethyl aluminum dichloride n-hexane solution (0.56 mmol) and 5 mL of n-heptane solvent are first subjected to a prepolymerization reaction, and are fully mixed at 22 ℃ for 90 min to prepare a prepolymerization liquid;

[0109] 2) Under the conditions of protective atmosphere and anaerobic anhydrous, first, 4-methyl-1-pentene (790 mmol) and 1-dodecene (338.57 mmol) were fed according to the constant ratio point, then the prepolymerization solution of step 1), hydrogen (22 kPaG) and n-heptane solvent (200 mL) were added into the reactor under the condition of 42℃ for 7h to obtain a polymerization solution;

[0110] 3) The above polymerization solution was quenched by using ethanol+water (1:1) mixed quencher as the quencher to obtain a 4-methyl-1-pentene / α-olefin copolymer.

[0111] In this embodiment, it can be known from the GPC-IR instrument that M w 、 It can be known that M w 、 The monomer reactivity ratio r1 of 4-methyl-1-pentene is 1.77, the monomer reactivity ratio r2 of 1-dodecene is 2.63, r1>1, r2>1, the binary copolymerization reaction has a constant ratio point, and the constant ratio point is 0.70. The high-temperature 13 C NMR can know that the content of 4-methyl-1-pentene unit in the 4-methyl-1-pentene / 1-dodecene copolymer is 0.70, which indicates that the constant ratio point polymerization is realized.

[0112]

Embodiment 8

[0113] A preparation method of a super-high-toughness 4-methyl-1-pentene / α-olefin copolymer, comprising the following steps:

[0114] 1) Under the conditions of protective atmosphere and anaerobic anhydrous, a small amount of 4-methyl-1-pentene (7.5 mmol), Z-N catalyst (1.5 μmol), isopropyl tert-butyl dimethoxysilane (21 μmol), 1 mol / L tri-n-pentyl aluminum n-hexane solution (0.21 mmol) and 5 mL n-heptane solvent were first subjected to prepolymerization, and were fully mixed at 28℃ for 150 min to prepare a prepolymerization solution;

[0115] 2) Under the conditions of protective atmosphere and anaerobic anhydrous, first, 4-methyl-1-pentene (790 mmol) and 1-tridecene (425.38 mmol) were fed according to the constant ratio point, then the prepolymerization solution of step 1), hydrogen (22 kPaG) and n-heptane solvent (200 mL) were added into the reactor under the condition of 55℃ for 9h to obtain a polymerization solution;

[0116] 3) The above polymerization solution was quenched by using propanol+butanol (1:1) mixed quencher as the quencher to obtain a 4-methyl-1-pentene / α-olefin copolymer.

[0117] In this embodiment, it can be known from the GPC-IR instrument that M w , It can be known that M w , The monomer reactivity ratio r1 of 4-methyl-1-pentene is 1.80, and the monomer reactivity ratio r2 of 1-tridecene is 2.49, r1>1, r2>1, the binary copolymerization reaction has a constant ratio point, and the constant ratio point is 0.65. High temperature 13 C NMR can know that the content of 4-methyl-1-pentene unit in the 4-methyl-1-pentene / 1-tridecene copolymer is 0.65, which indicates that the constant ratio point polymerization is realized.

[0118]

Embodiment 9

[0119] A preparation method of a super-high-toughness 4-methyl-1-pentene / α-olefin copolymer, comprising the following steps:

[0120] 1) Under the conditions of a protective atmosphere and anhydrous and anaerobic conditions, a small amount of 4-methyl-1-pentene (2 mmol), Z-N catalyst (0.5 μmol), cyclopentyl triethoxysilane (8 μmol), 1 mol / L isobutylaluminoxane n-hexane solution (0.085 mmol), and 5 mL of n-heptane solvent are first subjected to a prepolymerization reaction, and are fully mixed at 12°C for 20 min to prepare a prepolymerization liquid;

[0121] 2) Under the conditions of a protective atmosphere and anhydrous and anaerobic conditions, 4-methyl-1-pentene (790 mmol) and 1-tetradecene (526.67 mmol) are first fed according to the constant ratio point, and then the prepolymerization liquid of step 1), hydrogen (27 kPaG), and n-heptane solvent (200 mL) are added to the reactor and reacted at 32°C for 6 h to obtain a polymerization liquid;

[0122] 3) The above polymerization liquid is quenched by using octanol as a quenching agent to obtain a 4-methyl-1-pentene / α-olefin copolymer.

[0123] In this embodiment, it can be known from the GPC-IR instrument that M w , It can be known that M w , The monomer reactivity ratio r1 of 4-methyl-1-pentene is 1.93, and the monomer reactivity ratio r2 of 1-tetradecene is 2.35, r1>1, r2>1, the binary copolymerization reaction has a constant ratio point, and the constant ratio point is 0.60. High temperature 13 C NMR can know that the content of 4-methyl-1-pentene unit in the 4-methyl-1-pentene / 1-tetradecene copolymer is 0.60, which indicates that the constant ratio point polymerization is realized.

[0124] Example 10

[0125] A method for preparing a super-high-toughness 4-methyl-1-pentene / α-olefin copolymer, comprising the following steps:

[0126] 1) Under a protective atmosphere and in an oxygen-free and water-free condition, a small amount of 4-methyl-1-pentene (5 mmol), Z-N catalyst (0.8 μmol), cyclohexyltrimethoxysilane (12 μmol), 1 mol / L diisobutylaluminum oxide n-hexane solution (0.144 mmol), and 5 mL of n-heptane solvent are first subjected to a prepolymerization reaction, and are fully mixed at 33°C for 100 min to prepare a prepolymerization liquid;

[0127] 2) Under a protective atmosphere and in an oxygen-free and water-free condition, 4-methyl-1-pentene (790 mmol) and 1-pentadecene (646.36 mmol) are first fed according to a constant ratio point, and then the prepolymerization liquid of step 1), hydrogen (24 kPaG), and n-heptane solvent (200 mL) are added to a reactor and reacted at 58°C for 11 h to obtain a polymerization liquid;

[0128] 3) The polymerization liquid is quenched by using isooctanol as a quenching agent to obtain a 4-methyl-1-pentene / α-olefin copolymer.

[0129] In this example, it can be known from the GPC-IR instrument that M w 、 It can be known that M w 、 The monomer reactivity ratio r1 of 4-methyl-1-pentene is 2.01, the monomer reactivity ratio r2 of 1-pentadecene is 2.22, r1>1, r2>1, the binary copolymerization reaction has a constant ratio point, and the constant ratio point is 0.55. The high-temperature 13 C NMR can know that the content of 4-methyl-1-pentene units in the 4-methyl-1-pentene / 1-pentadecene copolymer is 0.55, which indicates that the constant ratio point polymerization is achieved.

[0130] Example 11

[0131] A method for preparing a super-high-toughness 4-methyl-1-pentene / α-olefin copolymer, comprising the following steps:

[0132] 1) Under a protective atmosphere and in an oxygen-free and water-free condition, a small amount of 4-methyl-1-pentene (2.5 mmol), Z-N catalyst (2.5 μmol), methyl dicyclopentylmethoxysilane (47.5 μmol), 1 mol / L methyl diethyl aluminum n-hexane solution (0.375 mmol), and 5 mL of n-heptane solvent are first subjected to a prepolymerization reaction, and are fully mixed at 18°C for 75 min to prepare a prepolymerization liquid;

[0133] 2) Under the conditions of protective atmosphere and anaerobic and anhydrous, 4-methyl-1-pentene (790 mmol) and 1-hexadecene (790 mmol) were first fed according to the constant ratio point, and then the prepolymerization solution of step 1), hydrogen (22 kPaG) and n-heptane solvent (200 mL) were added into the reactor under the condition of 38℃ for 13 h to obtain a polymerization solution;

[0134] 3) The above polymerization solution was quenched by water as a quenching agent to obtain a 4-methyl-1-pentene / α-olefin copolymer.

[0135] In this embodiment, it can be known from the GPC-IR instrument that M w , It can be known that M w , The monomer reactivity ratio r1 of 4-methyl-1-pentene is 1.0430, the monomer reactivity ratio r2 of 1-hexadecene is 1.0430, r1>1, r2>1, the binary copolymerization reaction has a constant ratio point, and the constant ratio point is 0.50. The high temperature 13 The C NMR can know that the content of 4-methyl-1-pentene unit in the 4-methyl-1-pentene / 1-hexadecene copolymer is 0.50, which indicates that the constant ratio point polymerization is realized.

[0136] [Embodiment 12]

[0137] A method for preparing a super-high-toughness 4-methyl-1-pentene / α-olefin copolymer, comprising the following steps:

[0138] 1) Under the conditions of protective atmosphere and anaerobic and anhydrous, a small amount of 4-methyl-1-pentene (3.2 mmol), Z-N catalyst (0.4 μmol), ethylcyclohexyldimethoxysilane (6.4 μmol), 1 mol / L diethyl-n-propylaluminum n-hexane solution (0.068 mmol) and 5 mL n-heptane solvent were first subjected to prepolymerization, and were fully mixed at 24℃ for 110 min to prepare a prepolymerization solution;

[0139] 2) Under the conditions of protective atmosphere and anaerobic and anhydrous, 4-methyl-1-pentene (790 mmol) and 1-heptadecene (965.56 mmol) were first fed according to the constant ratio point, and then the prepolymerization solution of step 1), hydrogen (21 kPaG) and n-heptane solvent (200 mL) were added into the reactor under the condition of 44℃ for 5 h to obtain a polymerization solution;

[0140] 3) The above polymerization solution was quenched by propanol as a quenching agent to obtain a 4-methyl-1-pentene / α-olefin copolymer.

[0141] In this embodiment, it can be known from the GPC-IR instrument that Mw 、 Mn w 、 , respectively, the monomer reactivity ratio of 4-methyl-1-pentene r1 is 2.22, the monomer reactivity ratio of 1-heptadecene r2 is 2.02, r1>1, r2>1, the binary copolymerization reaction has a constant ratio point, and the constant ratio point is 0.45. High temperature 13 C NMR shows that the content of 4-methyl-1-pentene units in the 4-methyl-1-pentene / 1-heptadecene copolymer is 0.45, indicating that the constant ratio point polymerization is achieved.

[0142] [Example 13]

[0143] A method for preparing a 4-methyl-1-pentene / α-olefin copolymer with ultrahigh toughness, comprising the following steps:

[0144] 1) Under the conditions of a protective atmosphere and anhydrous and oxygen-free, a small amount of 4-methyl-1-pentene (1.28 mmol), Z-N catalyst (8 μmol), triisopropylmethoxysilane (88 μmol), 1 mol / L triisopropylaluminum n-hexane solution (0.88 mmol), and 5 mL of n-heptane solvent are first subjected to a prepolymerization reaction, and are fully mixed at 26°C for 80 min to prepare a prepolymerization liquid;

[0145] 2) Under the conditions of a protective atmosphere and anhydrous and oxygen-free, 4-methyl-1-pentene (790 mmol) and 1-octadecene (1185 mmol) are first fed according to the constant ratio point, and then the prepolymerization liquid of step 1), hydrogen (21 kPa G), and n-heptane solvent (200 mL) are added to the reactor and reacted at 48°C for 14 h to obtain a polymerization liquid;

[0146] 3) The polymerization liquid is quenched by using butanol as a quenching agent to obtain a 4-methyl-1-pentene / α-olefin copolymer.

[0147] In this example, GPC-IR instrument shows that Mn w 、 Mn w 、 , respectively, the monomer reactivity ratio of 4-methyl-1-pentene r1 is 1.0430, the monomer reactivity ratio of 1-octadecene r2 is 1.0287, r1>1, r2>1, the binary copolymerization reaction has a constant ratio point, and the constant ratio point is 0.40. High temperature 13 C NMR shows that the content of 4-methyl-1-pentene units in the 4-methyl-1-pentene / 1-octadecene copolymer is 0.40, indicating that the constant ratio point polymerization is achieved.

[0148] [Example 14]

[0149] A preparation method of an ultrahigh toughness 4-methyl-1-pentene / α-olefin copolymer, comprising the following steps:

[0150] 1) Under a protective atmosphere and anaerobic and anhydrous conditions, a small amount of 4-methyl-1-pentene (4.8 mmol), Z-N catalyst (0.6 μmol), tert-butyl triethoxysilane (9 μmol), 1 mol / L triisopentyl aluminum n-hexane solution (0.096 mmol), and 5 mL of n-heptane solvent are first subjected to a prepolymerization reaction, and are fully mixed at 32°C for 130 min to prepare a prepolymerization liquid;

[0151] 2) Under a protective atmosphere and anaerobic and anhydrous conditions, 4-methyl-1-pentene (790 mmol) and 1-nonadecene (1467.14 mmol) are first fed according to a constant ratio point, and then the prepolymerization liquid of step 1), hydrogen (23 kPaG), and n-heptane solvent (200 mL) are added to a reactor and reacted at 52°C for 5.5 h to obtain a polymerization liquid;

[0152] 3) The polymerization liquid is quenched by using octanol as a quenching agent to obtain a 4-methyl-1-pentene / α-olefin copolymer.

[0153] In this embodiment, it can be known from the GPC-IR instrument that M w 、 It can be known that M w 、 The monomer reactivity ratio r1 of 4-methyl-1-pentene is 2.49, the monomer reactivity ratio r2 of 1-nonadecene is 1.81, r1>1, r2>1, the binary copolymerization reaction has a constant ratio point, and the constant ratio point is 0.35. High-temperature 13 C NMR can know that the content of 4-methyl-1-pentene units in the 4-methyl-1-pentene / 1-nonadecene copolymer is 0.35, which indicates that the constant ratio point polymerization is achieved.

[0154]

Example 15

[0155] A preparation method of an ultrahigh toughness 4-methyl-1-pentene / α-olefin copolymer, comprising the following steps:

[0156] 1) Under a protective atmosphere and anaerobic and anhydrous conditions, a small amount of 4-methyl-1-pentene (2.4 mmol), Z-N catalyst (0.4 μmol), diphenyl dimethoxysilane (4.5 μmol), 1 mol / L methyl di-n-butyl aluminum n-hexane solution (0.05 mmol), and 5 mL of n-heptane solvent are first subjected to a prepolymerization reaction, and are fully mixed at 15°C for 65 min to prepare a prepolymerization liquid;

[0157] 2) Under the conditions of protective atmosphere and anaerobic and anhydrous, 4-methyl-1-pentene (790 mmol) and 1-eicosene (1843.33 mmol) were fed according to the constant ratio point, and then the prepolymerization solution of step 1), hydrogen (24 kPaG) and n-heptane solvent (200 mL) were added into the reactor under the condition of 36℃ for 7.5 h to obtain a polymerization solution;

[0158] 3) The above polymerization solution was quenched by isooctanol as a quenching agent to obtain a 4-methyl-1-pentene / α-olefin copolymer.

[0159] In this embodiment, it can be known from the GPC-IR instrument that M w 、 It can be known that M w 、 The monomer reactivity ratio r1 of 4-methyl-1-pentene is 1.0430, the monomer reactivity ratio r2 of 1-eicosene is 1.0184, r1>1, r2>1, the binary copolymerization reaction has a constant ratio point, and the constant ratio point is 0.30. The high temperature 13 C NMR can know that the content of 4-methyl-1-pentene unit in the 4-methyl-1-pentene / 1-eicosene copolymer is 0.30, which indicates that the constant ratio point polymerization is realized.

[0160]

Comparative Example 1

[0161] A preparation method of a 4-methyl-1-pentene / α-olefin copolymer, which is only different from that of Example 1 in that it is not fed according to the constant ratio point, and the specific process is as follows:

[0162] 1) Under the conditions of protective atmosphere and anaerobic and anhydrous, a small amount of 4-methyl-1-pentene (0.8 mmol), Z-N catalyst (5 μmol), trimethylmethoxysilane (50 μmol), 1 mol / L triethylaluminum n-heptane solution (0.5 mmol) and 5 mL n-heptane solvent were first subjected to prepolymerization, and were fully mixed at 10℃ for 5 min to prepare a prepolymerization solution;

[0163] 2) Under the conditions of protective atmosphere and anaerobic and anhydrous, 4-methyl-1-pentene (790 mmol) and 1-hexene (42 mmol) were fed into the reactor (95:5), and then the prepolymerization solution of step 1), hydrogen (60 kPaG) and n-heptane solvent (200 mL) were added into the reactor under the condition of 30℃ for 15 h to obtain a polymerization solution;

[0164] 3) The above polymerization solution was quenched by ethanol as a quenching agent to obtain a 4-methyl-1-pentene / α-olefin copolymer.

[0165] In this comparative example, it can be known from the GPC-IR instrument that Mw 、 Mn= 100000, Mw= 7.18, r1= 1.04, r2= 3.10, r1>1, r2>1, the copolymerization reaction has a constant ratio point, the constant ratio point is 0.98. w 、 13 C NMR shows that the content of 4-methyl-1-pentene units in the 4-methyl-1-pentene / 1-hexene copolymer is 0.87, which is not a constant ratio point polymerization at this time.

[0166] [Comparative Example 2]

[0167] A method for preparing a 4-methyl-1-pentene / α-olefin copolymer, which is only different from Example 1 in that the feed is not according to the constant ratio point, as follows:

[0168] 1) Under the conditions of a protective atmosphere and anaerobic and anhydrous conditions, a small amount of 4-methyl-1-pentene (0.8 mmol), Z-N catalyst (5 μmol), trimethylmethoxysilane (50 μmol), 1 mol / L triethylaluminum in n-heptane solution (0.5 mmol), and 5 mL of n-heptane solvent were first subjected to a prepolymerization reaction, and were fully mixed at 10°C for 5 min to prepare a prepolymerization liquid;

[0169] 2) Under the conditions of a protective atmosphere and anaerobic and anhydrous conditions, 4-methyl-1-pentene (790 mmol) and 1-hexene (24 mmol) were fed into the reactor (97:3), and then the prepolymerization liquid in step 1), hydrogen (60 kPaG), and n-heptane solvent (200 mL) were added to the reactor at 30°C for 15 h to obtain a polymerization liquid;

[0170] 3) The above polymerization liquid was quenched by ethanol as a quenching agent to obtain a 4-methyl-1-pentene / α-olefin copolymer.

[0171] In this comparative example, GPC-IR instrument shows that Mn= 100000, Mw= 7.18, r1= 1.04, r2= 3.10, r1>1, r2>1, the copolymerization reaction has a constant ratio point, the constant ratio point is 0.98. w 、 w 、 13 C NMR shows that the content of 4-methyl-1-pentene units in the 4-methyl-1-pentene / 1-hexene copolymer is 0.93, which is not a constant ratio point polymerization at this time.

[0172] [Comparative Example 3]​​​

[0173] A preparation method of 4-methyl-1-pentene / α-olefin copolymer, which is only different from example 15 in that the constant ratio point is not used for feeding, and the specific process is as follows:

[0174] 1) Under the conditions of a protective atmosphere and anhydrous and anaerobic conditions, a small amount of 4-methyl-1-pentene (2.4 mmol), Z-N catalyst (0.4 μmol), diphenyldimethoxysilane (4.5 μmol), 1 mol / L methyl di-n-butyl aluminum in n-hexane (0.05 mmol) and 5 mL of n-heptane solvent are first subjected to a prepolymerization reaction, and are fully mixed at 15°C for 65 min to prepare a prepolymerization solution;

[0175] 2) Under the conditions of a protective atmosphere and anhydrous and anaerobic conditions, 4-methyl-1-pentene (790 mmol) and 1-eicosene (1185 mmol) are added to the reactor (40:60), and then the prepolymerization solution of step 1), hydrogen (24 kPaG) and n-heptane solvent (200 mL) are added to the reactor and reacted at 36°C for 7.5 h to obtain a polymerization solution;

[0176] 3) The above polymerization solution is quenched by using isooctanol as a quenching agent to obtain a 4-methyl-1-pentene / α-olefin copolymer.

[0177] It can be known from the GPC-IR instrument that M w 、 It can be known from the GPC-IR instrument that M w 、 , 255000 and 7.34, respectively, the monomer reactivity ratio r1 of 4-methyl-1-pentene is 2.63, the monomer reactivity ratio r2 of 1-hexene is 1.68, r1>1, r2>1, the binary copolymerization reaction has a constant ratio point, and the constant ratio point is 0.30. High temperature 13 C NMR can know that the content of 4-methyl-1-pentene unit in the 4-methyl-1-pentene / 1-hexene copolymer is 0.52, which is not a constant ratio point polymerization.

[0178] The comprehensive performance of the 4-methyl-1-pentene / α-olefin copolymer prepared in each example and comparative example is tested, and the results are shown in Table 1:

[0179] Table 1

[0180]

[0181]

[0182] As can be seen from the test results of Example 1 and Comparative Example 1 in Table 1, although the constant ratio point feeding of the present application has certain improvement on the mechanical strength and release property, the improvement on the toughness is particularly obvious, with the elongation at break and impact strength being improved by more than 5 times, thereby fundamentally solving the problem that the prior art is difficult to simultaneously improve the mechanical strength / release property and toughness.

[0183] The above only describes the preferred embodiments of the present application, and it should be noted that, for those skilled in the art, several improvements and supplements can be made without departing from the method of the present application, and these improvements and supplements should also be considered as the protection scope of the present application.

Claims

1. A method for preparing an ultra-high toughness 4-methyl-1-pentene / α-olefin copolymer, characterized in that, Includes the following steps: 1) The catalyst system, solvent, and a small amount of 4-methyl-1-pentene were thoroughly mixed for a period of time to prepare a prepolymer solution; 2) 4-methyl-1-pentene and α-olefin are fed into the reactor at a constant ratio point, and then the above prepolymer solution, solvent and optional molecular weight regulator are added into the reactor. After reacting for a period of time, a polymer solution is obtained. 3) The above polymerization solution was quenched with a quenching agent to obtain a 4-methyl-1-pentene / α-olefin copolymer; The catalyst system includes a main catalyst, a co-catalyst, and an external electron donor.

2. The method for preparing the ultra-high toughness 4-methyl-1-pentene / α-olefin copolymer according to claim 1, characterized in that, The main catalyst is a Ziegler-Natta catalyst; Preferably, the co-catalyst is one or more of the following: triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-pentylaluminum, triisopentylaluminum, methyl diethylaluminum, methyl di-n-propylaluminum, methyl diisopropylaluminum, methyl di-n-butylaluminum, methyl diisobutylaluminum, diethyl-n-propylaluminum, diethyl-n-butylaluminum, diethyl-isobutylaluminum, diethylaluminum chloride, ethyl dialuminum chloride, methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, propylaluminoxane, isobutylaluminoxane, and diisobutylaluminoxane. Preferably, the external electron donor is trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, triethylmethoxysilane, diethyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, phenyltriethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxysilane, isopropyltert-butyldimethoxysilane, cyclohexylmethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, cyclohexylmethoxysilane, dicyclopentyldimethoxysilane, diisopropyltert-butyldimethoxysilane, cyclohexylmethoxysilane, dicyclopentylmethoxysilane, di ... One or more of the following: pentyltriethoxysilane, cyclohexyltrimethoxysilane, methyldicyclopentylmethoxysilane, ethylcyclohexyldimethoxysilane, triisopropylmethoxysilane, tert-butyltriethoxysilane, diphenyldiethoxysilane, cycloheptyldimethoxysilane, methylphenyldiethoxysilane, diisopropyldiethoxysilane, cyclohexylisopropyldimethoxysilane, triphenylmethoxysilane, isobutylmethyldimethoxysilane, and n-butyltriethoxysilane.

3. The method for preparing the ultra-high toughness 4-methyl-1-pentene / α-olefin copolymer according to claim 1, characterized in that, The molar ratio of the main catalyst, external electron donor, and co-catalyst is 1:(10-20):(100-200).

4. The method for preparing the ultra-high toughness 4-methyl-1-pentene / α-olefin copolymer according to any one of claims 1-3, characterized in that, In step 1), the amount of 4-methyl-1-pentene fed is 160-8000 times that of the main catalyst, based on molar mass.

5. The method for preparing the ultra-high toughness 4-methyl-1-pentene / α-olefin copolymer according to any one of claims 1-4, characterized in that, In step 2), the amount of 4-methyl-1-pentene fed is 0.5 × 10⁻⁶ molars of the main catalyst. 5 -20×10 5 times.

6. The method for preparing the ultra-high toughness 4-methyl-1-pentene / α-olefin copolymer according to any one of claims 1-4, characterized in that, Preferably, the molecular weight regulator is hydrogen. Preferably, in step 2), a molecular weight regulator is added to control the system pressure to 20-60 kPaG.

7. The method for preparing the ultra-high toughness 4-methyl-1-pentene / α-olefin copolymer according to any one of claims 1-6, characterized in that, The solvent is one or more of n-hexane, n-heptane, and n-decane.

8. The method for preparing the ultra-high toughness 4-methyl-1-pentene / α-olefin copolymer according to any one of claims 1-7, characterized in that, In step 1), the reaction temperature is 10-35℃ and the reaction time is 5-180 min; Preferably, the reaction temperature in step 2) is 30-60℃ and the reaction time is 3-15h.

9. The method for preparing the ultra-high toughness 4-methyl-1-pentene / α-olefin copolymer according to any one of claims 1-8, characterized in that, The quenching agent is selected from one or more of water, ethanol, propanol, butanol, octanol, and isooctanol.

10. The method for preparing the ultra-high toughness 4-methyl-1-pentene / α-olefin copolymer according to any one of claims 1-9, characterized in that, The α-olefin is selected from C6-20 olefins, preferably one or more of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetracene, 1-tetradecene, 1-pentadecanene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecanene, and 1-eicosene.

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