Polybutylene-1 resin and preparation method thereof, polypropylene alloy material and preparation method and application thereof

Abstract

The invention relates to the technical field of macromolecules, in particular to polybutylene-1 resin and a preparation method thereof, a polypropylene alloy material and a preparation method and application thereof. The resin comprises a butene-1 structural unit and an alpha-olefin structural unit, wherein on the basis of the total weight of the polybutylene-1 resin, the content of the alpha-olefin structural unit is 5-11 wt%; wherein the melt index of the resin is 1-2g / 10min under the conditions that the temperature is 190 DEG C and the load is 2.16 kg; wherein the glass transition temperature of the resin is-30 DEG C to-44 DEG C. The polybutylene-1 resin has low glass transition temperature, the low-temperature toughness of the polypropylene alloy material is remarkably improved, the light transmittance of the polypropylene alloy material is improved, and the haze of the polypropylene alloy material is reduced.

Description

Technical Field

[0001] The present invention relates to the field of polymer technology, and particularly relates to a polybutene-1 resin and its preparation method, a polypropylene alloy material and its preparation method and application. Background Art

[0002] As the second largest general-purpose plastic, polypropylene has excellent properties such as high use temperature, good chemical stability and high strength. However, it also has defects such as poor low-temperature toughness and slightly insufficient transparency, and modification processing is often required for some transparent products used in low-temperature environments.

[0003] Sheet is one of the main product forms of polypropylene. It can be used for thermoforming to prepare food packaging products such as milk tea cups and cold chain trays, and can also be used to prepare daily necessities such as folders, document bags and coils through shearing and heat sealing. However, the above products have high requirements for the low-temperature toughness, light transmittance and haze of the products. Considering factors such as production cost and product flexibility, polypropylene homopolymer resin with a low melt index is generally used as a typical base material, such as drawing material T30S, and a certain amount of polyolefin toughening agent is additionally added to improve the low-temperature toughness of the product. Conventional polyolefin toughening agents, such as vinyl elastomers (POE) and propylene-based elastomers, often reduce the light transmittance and / or increase the haze of the product while toughening polypropylene, and a certain amount of clarifying agent needs to be additionally added to improve the transparency of the sheet. This method has production application problems such as high cost and complex processes.

[0004] CN107903499A discloses a transparent toughened modified polypropylene plastic, which uses metallocene polypropylene to toughen and improve the transparency of polypropylene, but does not disclose low-temperature toughness data, and the glass transition temperature of metallocene polypropylene is relatively high, so the improvement of the low-temperature toughness of the polypropylene substrate should be relatively limited.

[0005] Compared with other polyolefin materials, polybutene-1 resin has good creep resistance, environmental stress cracking resistance and impact resistance, and is very suitable for use as a pipe material. However, the conventional polybutene-1 resin has a relatively high glass transition temperature or poor mixing and processing performance with the polypropylene base material for sheets, and the toughening and transparency improvement effects on sheets are not good.

[0006] Therefore, there is an urgent need for a polybutene-1 resin that can improve the low-temperature toughness and light transmittance of polypropylene sheets and reduce the haze of polypropylene sheets. Summary of the Invention

[0007] The purpose of the present invention is to overcome the problems of poor low-temperature toughness, low light transmittance and high haze of polypropylene sheets existing in the prior art, and provide a polybutene-1 resin and its preparation method, a polypropylene alloy material and its preparation method and application. This polybutene-1 resin has a low glass transition temperature, can significantly improve the low-temperature toughness of the polypropylene alloy material, improve the light transmittance of the polypropylene alloy material, and reduce its haze.

[0008] To achieve the above object, a first aspect of the present invention provides a polybutene-1 resin, wherein the resin comprises a butene-1 structural unit and an α-olefin structural unit;

[0009] Wherein, based on the total weight of the polybutene-1 resin, the content of the α-olefin structural unit is 5-11 wt%;

[0010] Wherein, the melt index of the resin at 190 °C and a load of 2.16 kg is 1-2 g / 10 min;

[0011] Wherein, the glass transition temperature of the resin is -30 °C to -44 °C.

[0012] A second aspect of the present invention provides a method for preparing the polybutene-1 resin described in the first aspect above, wherein the method comprises:

[0013] Mixing a main catalyst, a cocatalyst and an electron donor, carrying out a polymerization reaction with butene-1 and α-olefins and hydrogen introduced under different pressures, and then adding an auxiliary agent to obtain the polybutene-1 resin.

[0014] A third aspect of the present invention provides a polypropylene alloy material, which comprises the polybutene-1 resin described in the first aspect above and a polypropylene resin.

[0015] A fourth aspect of the present invention provides a method for preparing the polypropylene alloy material described in the third aspect above, wherein the method comprises:

[0016] Mixing the polybutene-1 resin and the polypropylene resin, melting, extruding and pelletizing to obtain the polypropylene alloy material.

[0017] A fifth aspect of the present invention provides an application of the polypropylene alloy material described in the third aspect above or the polypropylene alloy material prepared by the method described in the fourth aspect above in food packaging products or daily necessities.

[0018] Through the above technical solutions, the present invention has the following beneficial effects:

[0019] (1) For the polybutene-1 resin provided by the present invention, the content of the α-olefin structural unit is 5-11 wt%, the melt index is 1-2 g / 10 min, and the glass transition temperature is -30 °C to -44 °C. The polybutene-1 resin with this structure has a special two-phase relationship with the polypropylene resin, which can improve the light transmittance of the polypropylene alloy material and reduce its haze; it has a low glass transition temperature, and the polypropylene alloy material obtained by blending with the polypropylene resin has excellent low-temperature toughness.

[0020] (2) The polybutene-1 resin provided by the present invention has a simple preparation method, can improve the low-temperature toughness and light transmittance of the polypropylene alloy material, reduce the haze of the polypropylene alloy material, and meet the requirements of more application markets for the polypropylene alloy material. Detailed Embodiments

[0021] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0022] In the first aspect of the present invention, a polybutene-1 resin is provided, wherein the resin comprises butene-1 structural units and α-olefin structural units;

[0023] Wherein, based on the total weight of the polybutene-1 resin, the content of the α-olefin structural units is 5-11 wt%.

[0024] Wherein, the melt index of the resin at 190 °C and a load of 2.16 kg is 1-2 g / 10 min;

[0025] Wherein, the glass transition temperature of the resin is -30 °C to -44 °C.

[0026] The inventors of the present invention have found that, compared with traditional polybutene-1 resins, the polybutene-1 resin of the present invention has a high matching degree of melt index with polypropylene resins for sheets, a low glass transition temperature, good molding processability, and the prepared polypropylene alloy material has good low-temperature toughness and transparency.

[0027] In some embodiments of the present invention, preferably, based on the total weight of the polybutene-1 resin, the content of the α-olefin structural units is 6-10 wt%.

[0028] In the present invention, preferably, based on the total weight of the polybutene-1 resin, the content of the butene-1 structural units is 88-94.9 wt%.

[0029] In the present invention, based on the total weight of the polybutene-1 resin, the content of the α-olefin structural unit is 5-11 wt%, which is beneficial to endowing the obtained polypropylene alloy material with excellent low-temperature toughness, high light transmittance and low haze. When the content of the α-olefin structural unit is greater than 11 wt%, there is too much α-olefin, resulting in a decrease in the light transmittance and an increase in the haze of the obtained polypropylene alloy material, and the light transmittance enhancement effect is poor. When the content ratio of the α-olefin structural unit is less than 5 wt%, there is too little α-olefin, resulting in insufficient low-temperature toughness of the obtained polypropylene alloy material and poor toughening effect. Preferably, the content of the α-olefin structural unit is 6-10 wt%, and the polypropylene alloy material has more excellent comprehensive properties.

[0030] In the present invention, the 1-butene is purchased from Dalian Dete Gas Co., Ltd., of polymerization grade with a purity of 99.9%; the α-olefin is purchased from Dalian Dete Gas Co., Ltd., of polymerization grade with a purity of 99.9%.

[0031] In some embodiments of the present invention, preferably, the melt index of the resin at 190 °C and a load of 2.16 kg is 1.2-1.7 g / 10 min.

[0032] In some embodiments of the present invention, preferably, the glass transition temperature of the resin is -35 °C to -43 °C.

[0033] In some embodiments of the present invention, preferably, the melt enthalpy of the resin is 15-30 J / g, preferably 16-28 J / g.

[0034] In some embodiments of the present invention, preferably, the molecular weight distribution (Mw / Mn) of the resin is 4.5-12, preferably 5-9.

[0035] In the present invention, the content of the α-olefin structural unit in the polybutene-1 resin is tested by infrared spectroscopy analysis.

[0036] In the present invention, the melt index of the polybutene-1 resin is determined according to the standard of 37199.2-2018, and the test conditions are 190 °C and a load of 2.16 kg.

[0037] In the present invention, the glass transition temperature of the polybutene-1 resin is tested by the DSC method. 7-9 mg of the sample is sealed into a DSC aluminum can, and then heated at a rate of 10 °C / min to 180 °C, and held at this temperature for 5 min to completely melt all the grains. Then it is cooled at a rate of 10 °C / min to -80 °C, held at a constant temperature for 5 min, and then heated at a rate of 10 °C / min to 180 °C. The plateau change temperature in this heating curve is taken as the glass transition temperature.

[0038] In the present invention, the melting enthalpy of the polybutene-1 resin is measured by DSC method. 7-9 mg of the sample is sealed in a DSC aluminum can, and then heated to 180 °C at a rate of 10 °C / min. It is held at this temperature for 5 min to completely melt all the crystal grains, and then cooled to 20 °C at a rate of 10 °C / min. After the polybutene-1 resin is crystallized and recrystallized at room temperature for 10 days, the aged sample is first cooled to -0 °C at a rate of 10 °C / min and held for 5 min, and then heated to 180 °C at a rate of 10 °C / min. The melting peak area in this round of heating is taken as its melting enthalpy.

[0039] In the present invention, the molecular weight distribution (Mw / Mn) of the polybutene-1 resin is measured by gel permeation chromatography (GPC). The molecular weight distribution curve is measured by a Waters 150-CALC / GPC system equipped with an infrared detector IR4POLIMERCHAR and a TSK column arrangement (GMHXL-HT type). At 135 °C, 1,2,4-trichlorobenzene (stabilized with 0.1 times the volume of 2,6-di-tert-butyl-p-cresol) is used as the solvent, the flow rate is 1 mL / min, and it is continuously stirred at 140 °C for 1 h. The sample is dissolved in 1,2,4-trichlorobenzene. The solution is filtered through a 0.45 μm polytetrafluoroethylene membrane, and the filtrate (concentration 0.08-1.2 g / L, injection volume 300 μL) is subjected to GPC, using monodisperse polystyrene as the standard sample.

[0040] In the present invention, the polybutene-1 resin with the content of α-olefin structural unit, melt index, glass transition temperature, melting enthalpy and molecular weight distribution within the above ranges has a special two-phase relationship with the polypropylene resin, which is beneficial to improving the light transmittance of the polypropylene alloy material and reducing its haze, and greatly improving the low-temperature toughness of the polypropylene alloy material. When the content of α-olefin structural unit, melt index, glass transition temperature, melting enthalpy and molecular weight distribution of the polybutene-1 resin are within the preferred ranges, it is more beneficial to improve the low-temperature toughness and light transmittance of the polypropylene alloy material and reduce the haze.

[0041] In some embodiments of the present invention, preferably, the α-olefin is selected from ethylene and / or propylene, and more preferably ethylene.

[0042] In some embodiments of the present invention, preferably, the resin further comprises: a main catalyst, a main catalyst, an electron donor and an auxiliary agent.

[0043] In the present invention, the type of the main catalyst can be selected from a relatively wide range, and can be various existing main catalysts suitable for preparing polyolefin-1 resins. Preferably, the main catalyst is a Ziegler-Natta catalyst.

[0044] In the present invention, the types of cocatalysts can be selected from a relatively wide range, and can be various existing cocatalysts applicable to the preparation of polyolefin-1 resins. Preferably, the cocatalyst is an alkyl aluminum, preferably selected from at least one of trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, and tri-n-butyl aluminum, and more preferably triisobutyl aluminum.

[0045] In the present invention, the electron donor can be a conventional electron donor in the art. In some embodiments of the present invention, preferably, the electron donor is an external electron donor of siloxane type, preferably selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, methyl tert-butyl dimethoxysilane, and cyclohexylmethyldimethoxysilane, and more preferably cyclohexylmethyldimethoxysilane.

[0046] In some embodiments of the present invention, preferably, based on the total weight of the polybutene-1 resin, the total amount of the main catalyst, cocatalyst, and electron donor is 0.015 - 0.2 wt%.

[0047] In the present invention, the total content of the main catalyst, cocatalyst, and electron donor is controlled by feeding.

[0048] In some embodiments of the present invention, preferably, the mass ratio of the main catalyst, cocatalyst, and electron donor is 0.01 - 0.02: 0.1 - 0.75: 0.1 - 0.8.

[0049] In some embodiments of the present invention, preferably, the additives include antioxidants and / or acid scavengers.

[0050] In the present invention, the types of antioxidants can be selected from a relatively wide range, and can be various existing substances applicable to improving the antioxidant performance of polyolefin-1 resins. Preferably, the antioxidant is selected from hindered phenol antioxidants and / or phosphite antioxidants, preferably selected from at least one of antioxidant 168, antioxidant 705T, antioxidant 1010, and antioxidant 1076.

[0051] In the present invention, the antioxidant is beneficial to improving the antioxidant property of the polybutene-1 resin and providing long-term use guarantee.

[0052] In the present invention, the acid scavenger is beneficial to neutralizing the acidic substances remaining in the Ziegler-Natta catalyst. The types of acid scavengers in the present invention can be selected from a relatively wide range, as long as the above object can be achieved, and can be various acid scavengers commonly used in the art. Preferably, the acid scavenger is selected from at least one of hydrotalcite, calcium stearate, and zinc stearate, and more preferably hydrotalcite. The acid scavenger in this preferred embodiment is beneficial to further improving the ability to neutralize the acidic substances remaining in the Ziegler-Natta catalyst.

[0053] In some embodiments of the present invention, preferably, based on the total amount of the polybutene-1 resin, the content of the auxiliary agent is 0.1-1 wt%.

[0054] In some embodiments of the present invention, preferably, the mass ratio of the antioxidant to the acid scavenger is 0.45-0.65:0.15-0.4. In the present invention, when the content of the antioxidant is low, the antioxidant effect is not significant; when the content of the antioxidant is too high, it is easy to cause yellowing of the product.

[0055] The present invention has no particular limitation on the sources of the main catalyst, cocatalyst, electron donor and auxiliary agent, which can be purchased commercially or prepared by existing methods.

[0056] The second aspect of the present invention provides a method for preparing the polybutene-1 resin described in the first aspect above, wherein the method includes:

[0057] In the presence of a solvent, the main catalyst, cocatalyst and electron donor are mixed, and subjected to a polymerization reaction with 1-butene and α-olefin and hydrogen introduced under different pressures, and then the auxiliary agent is added, and after drying, a polybutene-1 resin is obtained.

[0058] In the present invention, there is no particular limitation on the specific manner of mixing the above-mentioned main catalyst, cocatalyst, electron donor and solvent. They can be added sequentially, or some raw materials can be mixed first and then mixed with the remaining raw materials. In the present invention, preferably, the main catalyst suspension, cocatalyst solution and electron donor solution are mixed, and subjected to a polymerization reaction with 1-butene and α-olefin and hydrogen introduced under different pressures, and then the auxiliary agent is added, and after drying, a polybutene-1 resin is obtained.

[0059] In some embodiments of the present invention, preferably, the content of the main catalyst in the main catalyst suspension is 0.5-5 mg / mL, the content of the cocatalyst in the cocatalyst solution is 0.15-0.5 mol / L, and the content of the electron donor in the electron donor solution is 0.5-1.5 mol / L.

[0060] In the present invention, the main catalyst suspension, cocatalyst solution and electron donor solution can be prepared by diluting with a solvent. Preferably, the solvents in the main catalyst suspension, cocatalyst solution and electron donor solution are inert organic solvents, preferably selected from at least one of white oil, n-hexane, n-octane, isohexane and heptane, and more preferably n-hexane.

[0061] In some embodiments of the present invention, preferably, the polymerization reaction comprises two stages: in the first stage, the pressure of introducing α-olefin is 0.8 - 2 bar, the pressure of introducing hydrogen is 0.5 - 1 bar, and the time of the first stage is 0.5 - 2.5 h; in the second stage, the pressure of introducing α-olefin is 0.8 - 2 bar, the pressure of introducing hydrogen is 0.5 - 1 bar, and the time of the second stage is 0.5 - 2.5 h; the temperature of the polymerization reaction is 70 - 80 °C. In the present invention, controlling the conditions of the polymerization reaction within the above ranges is beneficial to making the prepared polybutene-1 resin have a melt index of 1 - 2 g / 10 min at 190 °C and a load of 2.16 kg, a glass transition temperature of -30 °C to -44 °C, and based on the total weight of the polybutene-1 resin, the content of α-olefin structural units is 5 - 11 wt%.

[0062] In the present invention, the polymerization reaction can be carried out in a continuous or batch form. Batch polymerization can be carried out in an autoclave equipped with a stirring and temperature device. The content of α-olefin structural units is controlled by controlling the partial pressure of α-olefin, the melt index of the resin is controlled by controlling the partial pressure of hydrogen, and the molecular weight distribution is controlled by changing the reaction conditions of the two stages.

[0063] In the present invention, hydrogen is used as the melt index regulator in the polymerization process, that is, according to the requirements of the polybutene-1 resin, the addition amounts of α-olefin and hydrogen in the polymerization autoclave are controlled to adjust the content of α-olefin structural units, melt index, glass transition temperature, melt enthalpy, and molecular weight distribution of the polybutene-1 resin. The hydrogen is purchased from Dalian Dete Gas Co., Ltd. with a purity of 99.9%.

[0064] In the present invention, preferably, the preparation method of the polybutene-1 resin comprises: first diluting the Ziegler-Natta catalyst, alkylaluminum cocatalyst, and siloxane external electron donor with n-hexane, and then sequentially adding butene-1, the Ziegler-Natta catalyst, alkylaluminum cocatalyst, and siloxane external electron donor suspension or solution into the autoclave; at the polymerization reaction temperature, introducing α-olefin and hydrogen to carry out the polymerization reaction in the first stage, and continuing to introduce α-olefin and hydrogen to carry out the second polymerization reaction. After the polymerization reaction is completed, an antioxidant, an acid scavenger, and a deactivator are injected into the autoclave to be mixed with the polymer solution to deactivate the active centers, and at the same time, the antioxidant and the acid scavenger are fully mixed with the polymer solution. After washing, filtering, and drying, the polybutene-1 resin is obtained.

[0065] In the present invention, the deactivator is conducive to deactivating the active substances in the polymer solution, efficiently terminating the polymerization reaction, and preventing problems of polymerization or explosive polymerization in subsequent treatment processes. The deactivator can be a conventional deactivator in the art, and can be selected from any one of water, oxygen, carbon dioxide or carbon monoxide, preferably water, and the water is preferably deionized water. The mass ratio of the deactivator to the cocatalyst is 1 - 50:1.

[0066] In the present invention, the conditions for washing are not particularly limited, and washing with ethanol is preferred; the conditions for drying are not specifically limited, and drying in a vacuum drying oven at 50 - 60°C for 8 - 12 h is preferred.

[0067] The third aspect of the present invention provides a polypropylene alloy material, which includes the polybutene-1 resin and polypropylene resin described in the first aspect above.

[0068] In some embodiments of the present invention, preferably, based on the total amount of the polypropylene alloy material, the content of the polybutene-1 resin is 3 - 7.5 wt%.

[0069] In the present invention, controlling the content of the polybutene-1 resin within the above range is conducive to making the prepared polypropylene alloy material have excellent low-temperature toughness, high light transmittance and low haze.

[0070] In some embodiments of the present invention, preferably, the Charpy impact strength of the material at room temperature (25°C) is 5 - 8 kJ / m 2 ; the Charpy impact strength at -10°C is 1.5 - 2.5 kJ / m 2 ; the flexural modulus is 1150 - 1400 MPa; the light transmittance of a 1 mm thin plate is 90 - 92%; the haze is 35 - 45.

[0071] In the present invention, the Charpy impact strength of the polypropylene alloy material is tested according to the method of GB / T1043.1 - 2008. Under the conditions of 200°C and 5 MPa, a rectangular sample bar of 4 mm×10 mm×80 mm is injection-molded for 45 s, and a Type A notch is machined on the rectangular sample bar. After storing in a constant temperature and humidity chamber for 48 h, the Charpy notched impact strength at room temperature (25°C) is measured. Among them, for the impact strength at -10°C, the test sample bar needs to be kept at a constant temperature in a -10°C refrigerator for 2 h.

[0072] In the present invention, the flexural modulus of the polypropylene alloy material is tested according to the method of GB / T 9341 - 2008. Under the conditions of 200°C and 5 MPa, a rectangular sample bar of 4 mm×10 mm×80 mm is injection-molded for 45 s, and after storing in a constant temperature and humidity chamber for 48 h, the flexural modulus is measured.

[0073] In the present invention, the light transmittance and haze of the polypropylene alloy material are tested according to the method of GB / T 2410-2008. Under the conditions of 200 °C and 5 MPa, an injection molding is carried out for 45 s to prepare a 1-mm thin plate specimen, which is stored in a constant temperature and humidity chamber for 48 h, and then the light transmittance and haze are tested.

[0074] In the present invention, the polypropylene alloy material has excellent low-temperature toughness compared with traditional polypropylene materials, has high light transmittance and low haze, and meets the requirements of more application markets for polypropylene alloy materials.

[0075] The fourth aspect of the present invention provides a method for preparing the polypropylene alloy material described in the third aspect above, wherein the method includes:

[0076] Mixing a polybutene-1 resin and a polypropylene resin, followed by melting, extrusion, and pelletizing to obtain the polypropylene alloy material. In some embodiments of the present invention, preferably, the extrusion temperature is 180-250 °C.

[0077] In the present invention, preferably, the polypropylene resin and the polybutene-1 resin are added to a high-speed mixer and mixed for 2-5 min under the condition of 2000-2200 rpm to obtain a premix; the premix is fed into the main feeding port of a twin-screw extruder and undergoes melting, extrusion, pelletizing, and homogenization, wherein the conveying temperature is 180-200 °C, the homogenization temperature is 210-250 °C, the extrusion temperature is 190-220 °C, and the die temperature is 200-230 °C to obtain a polypropylene alloy material. The shape of the polypropylene alloy material is not particularly limited, and it is preferably a polypropylene alloy material for sheets. The polypropylene resin is purchased from Sinopec Zhenhai Refining & Chemical, with the grade of T30S, a melt index of 3.5 g / 10 min at 230 °C and a load of 2.16 kg, and a density of 0.91 g / mL.

[0078] The substances, equipment, and process parameters not defined in the present invention can be selected according to the prior art and belong to the conventional technical means in the art.

[0079] The fifth aspect of the present invention provides an application of the polypropylene alloy material described in the third aspect above or the polypropylene alloy material prepared by the method described in the fourth aspect above in food packaging products or daily necessities.

[0080] In the present invention, preferably, the polypropylene alloy material is particularly suitable for the preparation of milk tea cups, cold chain trays, file folders, and document bags.

[0081] In the present invention, unless otherwise specified, normal temperature refers to "25 °C".

[0082] The present invention will be described in detail below through examples.

[0083] In the following examples and comparative examples, the test methods for the melt index, molecular weight distribution, bonded ethylene content, glass transition temperature, and melting enthalpy of polybutene-1 resins are the same as those in the specific implementation manner; the test methods for the notched Izod impact strength, flexural modulus, light transmittance, and haze of the polypropylene alloy material at normal temperature (20°C) and -10°C are the same as those in the specific implementation manner, and will not be elaborated here.

[0084] The raw materials used in the following examples and comparative examples are as follows:

[0085] Main catalyst: Ziegler-Natta catalyst, purchased from Beijing Research Institute of Chemical Industry;

[0086] Cocatalyst: triisobutylaluminum, purchased from Beijing Huawei Ruike;

[0087] Donor: cyclohexylmethyldimethoxysilane, purchased from Anychem;

[0088] 1-butene: purchased from Dalian Dete Gas Co., Ltd., polymerization grade, purity 99.9%;

[0089] Ethylene: purchased from Dalian Dete Gas Co., Ltd., polymerization grade, purity 99.9%;

[0090] Hydrogen: purchased from Dalian Dete Gas Co., Ltd., purity 99.9%;

[0091] Antioxidant: purchased from Ningbo Yuyue New Material Technology Co., Ltd.;

[0092] Acid scavenger: purchased from Ningbo Yuyue New Material Technology Co., Ltd.;

[0093] Toughening agent - 1: POE, with 1-butene as the second comonomer, grade DF 740, purchased from Mitsui Chemicals, melt index at 190°C and load of 2.16 kg is 3.6 g / 10 min, melt index at 230°C and load of 2.16 kg is 6.7 g / 10 min, density 0.87 g / mL;

[0094] Toughening agent - 2: POP, with 1-octene as the second comonomer, grade Supreme 021, purchased from SK Chemicals, melt index at 190°C and load of 2.16 kg is 1 g / 10 min, melt index at 230°C and load of 2.16 kg is 2.5 g / 10 min, density 0.9 g / mL;

[0095] Toughening agent - 3: Propylene - based elastomer, grade 3000, purchased from ExxonMobil, melt index at 190°C and load of 2.16 kg is 3.7 g / 10 min, melt index at 230°C and load of 2.16 kg is 8 g / 10 min, density is 0.87 g / mL;

[0096] Toughening agent - 4: Propylene - based elastomer, grade 6102, purchased from ExxonMobil, melt index at 190°C and load of 2.16 kg is 1.4 g / 10 min, melt index at 230°C and load of 2.16 kg is 8 g / 10 min, density is 0.86 g / mL;

[0097] Toughening agent - 5: Metallocene polypropylene, grade EX6000, purchased from Japan Polypropylene Corporation, melt index at 230°C and load of 2.16 kg is 2.9 g / 10 min, density is 0.9 g / mL;

[0098] Polypropylene resin: Homopolypropylene, grade T30S, purchased from Sinopec Zhenhai Refining & Chemical Company, melt index at 230°C and load of 2.16 kg is 3.5 g / 10 min, density is 0.91 g / mL.

[0099] Example 1

[0100] (1) Under the conditions of a temperature of 140°C and high vacuum, activate a 3 - L autoclave for 2 h. After the temperature of the autoclave drops to room temperature, add 1200 g of butene - 1, 3 mL of a hexane suspension of Ziegler - Natta catalyst (5 mg / mL), 7 mL of a hexane solution of triisobutylaluminum (0.1 mol / L), and 3.5 mL of a hexane solution of cyclohexylmethyldimethoxysilane (0.5 mol / L) into the autoclave. Then raise the temperature of the autoclave to 75°C. In the first polymerization stage, introduce hydrogen into the autoclave at a pressure of 0.5 bar, and then introduce ethylene at a pressure of 0.8 bar, and continuously react for 1 h. Then in the second polymerization stage, continue to introduce hydrogen at a pressure of 0.5 bar, and then introduce ethylene at a pressure of 0.8 bar, and continuously react for 1 h. After polymerization is completed, mix the obtained polymer solution with 0.1 g of antioxidant 1010, 0.2 g of antioxidant 168, 0.2 g of hydrotalcite, and 5 mL of deionized water in a mixer to terminate the reaction. After washing, filtering, and drying, 300 g of polybutene - 1 - type resin is obtained;

[0101] (2) The polypropylene resin (T30S) and the polybutene-1 resin are added to a high-speed mixer at a mass ratio of 19:1 and mixed for 2 min. Then, the obtained premix is fed into the main feeding port of a twin-screw extruder and subjected to melting, extrusion, granulation, and homogenization. Among them, the total time for melting, extrusion, and granulation is 10 min, the conveying temperature is 180 °C, the homogenization temperature is 220 °C, the extrusion temperature is 220 °C, and the die temperature is 200 °C, obtaining a polypropylene alloy material for sheets.

[0102] The ethylene structural unit content, melt index, molecular weight distribution, glass transition temperature, and melting enthalpy of the polybutene-1 resin are shown in Table 1;

[0103] The results of the notched Izod impact strength, flexural modulus, light transmittance, and haze of the polypropylene alloy material at room temperature (25 °C) and -10 °C are shown in Table 2.

[0104] Example 2

[0105] (1) Under the conditions of a temperature of 140 °C and high vacuum, a 3 L autoclave is activated for 2 h. After the temperature of the autoclave drops to room temperature, 1200 g of butene-1, 3 mL of a hexane suspension of a Ziegler-Natta catalyst (5 mg / mL), 7 mL of a hexane solution of triisobutylaluminum (0.1 mol / L), and 3.5 mL of a hexane solution of cyclohexylmethyldimethoxysilane (0.5 mol / L) are added into the autoclave. Then, the temperature of the autoclave is raised to 75 °C. In the first polymerization stage, hydrogen is introduced into the autoclave at a pressure of 0.5 bar, and then ethylene is introduced at a pressure of 2 bar, and the reaction is continuously carried out for 0.8 h. Then, in the second polymerization stage, hydrogen is introduced at a pressure of 1 bar, and then ethylene is introduced at a pressure of 2 bar, and the reaction is continuously carried out for another 1.2 h; after the polymerization is completed, the obtained polymer solution is mixed with 0.15 g of antioxidant 1076, 0.15 g of antioxidant 705T, 0.1 g of calcium stearate, and 5 mL of deionized water in a mixer to terminate the reaction. After washing, filtering, and drying, 317 g of polybutene-1 resin is obtained;

[0106] (2) The polypropylene resin (T30S) and the polybutene-1 resin are added to a high-speed mixer at a mass ratio of 19:1 and mixed for 2 min. Then, the obtained premix is fed into the main feeding port of a twin-screw extruder and subjected to melting, extrusion, granulation, and homogenization. Among them, the total time for melting, extrusion, and granulation is 10 min, the conveying temperature is 180 °C, the homogenization temperature is 230 °C, the extrusion temperature is 220 °C, and the die temperature is 200 °C, obtaining a polypropylene alloy material for sheets.

[0107] The ethylene structural unit content, melt index, molecular weight distribution, glass transition temperature, and melting enthalpy of the polybutene-1 resin are shown in Table 1;

[0108] The results of the notched Izod impact strength, flexural modulus, light transmittance, and haze of the polypropylene alloy material at room temperature (25°C) and -10°C are shown in Table 2.

[0109] Example 3

[0110] According to the method of Example 1, the difference is that

[0111] In step (1), the hydrogen pressure introduced in the first polymerization stage is 0.5 bar, the ethylene pressure is 1.3 bar, and the polymerization time is 1.5 h; in the second polymerization stage, the hydrogen pressure introduced is 0.8 bar, the ethylene pressure is 1.3 bar, and the polymerization time is 0.8 h; 299 g of polybutene-1 resin is obtained.

[0112] The ethylene structural unit content, melt index, molecular weight distribution, glass transition temperature, and melting enthalpy of the polybutene-1 resin are shown in Table 1;

[0113] The results of the notched Izod impact strength, flexural modulus, light transmittance, and haze of the polypropylene alloy material at room temperature (25°C) and -10°C are shown in Table 2.

[0114] Example 4

[0115] According to the method of Example 1, the difference is that

[0116] In step (1), the hydrogen pressure introduced in the first polymerization stage is 0.5 bar, the ethylene pressure is 1.4 bar, and the polymerization time is 1.5 h; in the second polymerization stage, the hydrogen pressure introduced is 0.8 bar, the ethylene pressure is 1.4 bar, and the polymerization time is 1 h; 302 g of polybutene-1 resin is obtained.

[0117] The ethylene structural unit content, melt index, molecular weight distribution, glass transition temperature, and melting enthalpy of the polybutene-1 resin are shown in Table 1;

[0118] The results of the notched Izod impact strength, flexural modulus, light transmittance, and haze of the polypropylene alloy material at room temperature (25°C) and -10°C are shown in Table 2.

[0119] Example 5

[0120] According to the method of Example 1, the difference is that

[0121] In step (1), the hydrogen pressure introduced in the first polymerization stage is 0.5 bar, the ethylene pressure is 1.3 bar, and the polymerization time is 1.5 h; in the second polymerization stage, the hydrogen pressure introduced is 0.8 bar, the ethylene pressure is 1.5 bar, and the polymerization time is 1 h; 307 g of polybutene-1 resin is obtained.

[0122] The ethylene structural unit content, melt index, molecular weight distribution, glass transition temperature, and melting enthalpy of the polybutene-1 resin are shown in Table 1;

[0123] The results of the notched Izod impact strength, flexural modulus, light transmittance, and haze of the polypropylene alloy material at room temperature (25°C) and -10°C are shown in Table 2.

[0124] Example 6

[0125] According to the method of Example 1, the difference is that

[0126] In step (1), the hydrogen pressure introduced in the first polymerization stage is 0.5 bar, the ethylene pressure is 1.3 bar, and the polymerization time is 1.5 h; in the second polymerization stage, the hydrogen pressure introduced is 0.8 bar, the ethylene pressure is 1.5 bar, and the polymerization time is 1 h; 296 g of polybutene-1 resin is obtained;

[0127] In step (2), the mass ratio of the polypropylene resin (T30S) to the polybutene-1 resin is 92.5:7.5.

[0128] The ethylene structural unit content, melt index, molecular weight distribution, glass transition temperature, and melting enthalpy of the polybutene-1 resin are shown in Table 1;

[0129] The results of the notched Izod impact strength, flexural modulus, light transmittance, and haze of the polypropylene alloy material at room temperature (25°C) and -10°C are shown in Table 2.

[0130] Comparative Example 1

[0131] (1) Under the conditions of a temperature of 140°C and high vacuum, activate a 3 L autoclave for 2 h. After the temperature of the autoclave drops to room temperature, add 1200 g of butene-1, 3 mL of a hexane suspension of Ziegler-Natta catalyst (5 mg / mL), 7 mL of a hexane solution of triisobutylaluminum (0.1 mol / L), and 3.5 mL of a hexane solution of cyclohexylmethyldimethoxysilane (0.5 mol / L) into the autoclave. Then raise the temperature of the autoclave to 75°C. In the first polymerization stage, introduce hydrogen into the autoclave at a pressure of 0.2 bar, and then introduce ethylene at a pressure of 0.9 bar, and continuously react for 2.5 h. Then, in the second polymerization stage, continue to introduce hydrogen at a pressure of 0.2 bar, and then introduce ethylene at a pressure of 0.9 bar, and continuously react for another 0.5 h; after the polymerization is completed, mix the obtained polymer solution with 0.2 g of antioxidant 1010, 0.2 g of antioxidant 705T, 0.15 g of hydrotalcite, and 5 mL of deionized water in a mixer to terminate the reaction. After washing, filtering, and drying, 311 g of polybutene-1 resin is obtained;

[0132] (2) Add polypropylene resin (T30S) and the polybutene-1 resin in a mass ratio of 19:1 to a high-speed mixer and mix for 2 min. Then feed the obtained premix into the main feeding port of a twin-screw extruder, and conduct melting, extrusion, granulation, and homogenization. Among them, the total time for melting, extrusion, and granulation is 10 min, the conveying temperature is 180 °C, the homogenization temperature is 220 °C, the extrusion temperature is 220 °C, and the die temperature is 200 °C to obtain a polypropylene alloy material for sheets.

[0133] The ethylene structural unit content, melt index, molecular weight distribution, glass transition temperature, and melting enthalpy of the polybutene-1 resin are shown in Table 1;

[0134] The results of the notched Izod impact strength, flexural modulus, light transmittance, and haze of the polypropylene alloy material at room temperature (25 °C) and -10 °C are shown in Table 2.

[0135] Comparative Example 2

[0136] (1) Activate a 3 L autoclave at 140 °C under high vacuum for 2 h. After the temperature of the autoclave drops to room temperature, add 1200 g of butene-1, 3 mL of a hexane suspension (5 mg / mL) of a Ziegler-Natta catalyst, 7 mL of a hexane solution (0.1 mol / L) of triisobutylaluminum, and 3.5 mL of a hexane solution (0.5 mol / L) of cyclohexylmethyldimethoxysilane to the autoclave. Then raise the temperature of the autoclave to 75 °C, introduce hydrogen into the autoclave at a pressure of 1.2 bar, and then introduce ethylene at a pressure of 1.5 bar, and continuously react for 1 h. Then introduce hydrogen at a pressure of 1.5 bar, and then introduce ethylene at a pressure of 1.5 bar, and continuously react for 1 h again; after the polymerization is completed, mix the obtained polymer solution with 0.2 g of antioxidant 1010, 0.2 g of antioxidant 705T, 0.1 g of hydrotalcite, and 5 mL of deionized water in a mixer to terminate the reaction. After washing, filtering, and drying, 315 g of polybutene-1 resin is obtained;

[0137] (2) Add polypropylene resin (T30S) and the polybutene-1 resin in a mass ratio of 19:1 to a high-speed mixer and mix for 2 min. Then feed the obtained premix into the main feeding port of a twin-screw extruder, and conduct melting, extrusion, granulation, and homogenization. Among them, the total time for melting, extrusion, and granulation is 10 min, the conveying temperature is 180 °C, the homogenization temperature is 220 °C, the extrusion temperature is 220 °C, and the die temperature is 200 °C to obtain a polypropylene alloy material for sheets.

[0138] The ethylene structural unit content, melt index, molecular weight distribution, glass transition temperature, and melting enthalpy of the polybutene-1 resin are shown in Table 1;

[0139] The results of the notched Izod impact strength, flexural modulus, light transmittance, and haze of the polypropylene alloy material at room temperature (25 °C) and -10 °C are shown in Table 2.

[0140] Comparative Example 3

[0141] According to the method of Example 1, the difference is that

[0142] In step (1), hydrogen was introduced into the autoclave at a pressure of 0.5 bar, and then ethylene was introduced at a pressure of 0.2 bar, and the continuous reaction was carried out for 2 h. Then, hydrogen was introduced at a pressure of 0.7 bar, and then ethylene was introduced at a pressure of 0.2 bar, and the continuous reaction was carried out for another 0.5 h; 290 g of polybutene-1 resin was obtained.

[0143] The ethylene structural unit content, melt index, molecular weight distribution, glass transition temperature, and melting enthalpy of the polybutene-1 resin are shown in Table 1;

[0144] The results of the notched Izod impact strength, flexural modulus, light transmittance, and haze of the polypropylene alloy material at room temperature (25 °C) and -10 °C are shown in Table 2.

[0145] Comparative Example 4

[0146] According to the method of Example 1, the difference is that

[0147] In step (1), hydrogen was introduced into the autoclave at a pressure of 0.5 bar, and then ethylene was introduced at a pressure of 3.2 bar, and the continuous reaction was carried out for 1.5 h. Then, hydrogen was introduced at a pressure of 0.7 bar, and then ethylene was introduced at a pressure of 3.2 bar, and the continuous reaction was carried out for another 1 h; 320 g of polybutene-1 resin was obtained.

[0148] The ethylene structural unit content, melt index, molecular weight distribution, glass transition temperature, and melting enthalpy of the polybutene-1 resin are shown in Table 1;

[0149] The results of the notched Izod impact strength, flexural modulus, light transmittance, and haze of the polypropylene alloy material at room temperature (25 °C) and -10 °C are shown in Table 2.

[0150] Comparative Example 5

[0151] Polypropylene resin (T30S) and toughening agent-1 were added to a high-speed mixer at a mass ratio of 19:1 and mixed for 2 min. Then, the obtained premix was fed into the main feeding port of a twin-screw extruder and subjected to melting, extrusion, granulation, and homogenization. Among them, the total time of melting, extrusion, and granulation was 10 min, the conveying temperature was 180 °C, the homogenization temperature was 220 °C, the extrusion temperature was 220 °C, and the die temperature was 200 °C to obtain a polypropylene alloy material for sheets.

[0152] The results of the notched Izod impact strength, flexural modulus, light transmittance, and haze of the polypropylene alloy material at room temperature (25°C) and -10°C are shown in Table 2.

[0153] Comparative Example 6

[0154] Polypropylene resin (T30S) and toughening agent -2 were added to a high-speed mixer at a mass ratio of 19:1 and mixed for 2 minutes. Then, the obtained premix was fed into the main feeding port of a twin-screw extruder and subjected to melting, extrusion, pelletizing, and homogenization. Among them, the total time for melting, extrusion, and pelletizing was 10 minutes, the conveying temperature was 180°C, the homogenization temperature was 220°C, the extrusion temperature was 220°C, and the die temperature was 200°C to obtain a polypropylene alloy material for sheets.

[0155] The results of the notched Izod impact strength, flexural modulus, light transmittance, and haze of the polypropylene alloy material at room temperature (25°C) and -10°C are shown in Table 2.

[0156] Comparative Example 7

[0157] Polypropylene resin (T30S) and toughening agent -3 were added to a high-speed mixer at a mass ratio of 19:1 and mixed for 2 minutes. Then, the obtained premix was fed into the main feeding port of a twin-screw extruder and subjected to melting, extrusion, pelletizing, and homogenization. Among them, the total time for melting, extrusion, and pelletizing was 10 minutes, the conveying temperature was 180°C, the homogenization temperature was 220°C, the extrusion temperature was 220°C, and the die temperature was 200°C to obtain a polypropylene alloy material for sheets.

[0158] The results of the notched Izod impact strength, flexural modulus, light transmittance, and haze of the polypropylene alloy material at room temperature (25°C) and -10°C are shown in Table 2.

[0159] Comparative Example 8

[0160] Polypropylene resin (T30S) and toughening agent -4 were added to a high-speed mixer at a mass ratio of 19:1 and mixed for 2 minutes. Then, the obtained premix was fed into the main feeding port of a twin-screw extruder and subjected to melting, extrusion, pelletizing, and homogenization. Among them, the total time for melting, extrusion, and pelletizing was 10 minutes, the conveying temperature was 180°C, the homogenization temperature was 220°C, the extrusion temperature was 220°C, and the die temperature was 200°C to obtain a polypropylene alloy material for sheets.

[0161] The results of the notched Izod impact strength, flexural modulus, light transmittance, and haze of the polypropylene alloy material at room temperature (25°C) and -10°C are shown in Table 2.

[0162] Comparative Example 9

[0163] The polypropylene resin (T30S) and toughening agent - 5 were added to a high - speed mixer in a mass ratio of 19:1 and mixed for 2 min. Then the obtained premix was fed into the main feeding port of a twin - screw extruder and subjected to melting, extrusion, pelletizing and homogenization. Among them, the total time of melting, extrusion and pelletizing was 10 min, the conveying temperature was 180 °C, the homogenization temperature was 220 °C, the extrusion temperature was 220 °C, and the die temperature was 200 °C, obtaining a polypropylene alloy material for sheets.

[0164] The results of the notched Izod impact strength, flexural modulus, light transmittance and haze of the polypropylene alloy material at room temperature (25 °C) and - 10 °C are shown in Table 2.

[0165] Comparative Example 10

[0166] The polypropylene resin (T30S) was added to a high - speed mixer and mixed for 2 min. Then the obtained premix was fed into the main feeding port of a twin - screw extruder and subjected to melting, extrusion, pelletizing and homogenization. Among them, the total time of melting, extrusion and pelletizing was 10 min, the conveying temperature was 180 °C, the homogenization temperature was 220 °C, the extrusion temperature was 220 °C, and the die temperature was 200 °C, obtaining a polypropylene alloy material for sheets.

[0167] The results of the notched Izod impact strength, flexural modulus, light transmittance and haze of the polypropylene alloy material at room temperature (25 °C) and - 10 °C are shown in Table 2.

[0168] Table 1

[0169]

[0170] Table 2

[0171]

[0172] As can be seen from the results in Table 1, the polybutene-1 resin obtained by the method of the present invention has a melt index of 1-2 g / 10 min, a molecular weight distribution (Mw / Mn) of 4.5-12, an ethylene content of 5-11 wt%, a glass transition temperature of -35°C to -44°C, and a melting enthalpy of 15-30 J / g, having a low melting enthalpy (low crystallinity) and a low glass transition temperature. Combining the data of Examples 1-6 and Table 2, it can be seen that the polypropylene alloy material prepared from the polybutene-1 resin provided by the present invention has a relatively high Charpy impact strength at room temperature (25°C) and -10°C, and has a high light transmittance and a low haze; the polybutene-1 resin used in Comparative Example 1 has a relatively low melt index, and the obtained polypropylene alloy material has a low light transmittance and a high haze; the polybutene-1 resin used in Comparative Example 2 has a relatively high melt index, and the obtained polypropylene alloy material has poor mechanical properties; the polybutene-1 resin used in Comparative Example 3 has a relatively low ethylene content and glass transition temperature and a relatively high melting enthalpy, and the obtained polypropylene alloy material has poor mechanical properties; the polybutene-1 resin used in Comparative Example 4 has an excessively high bonded ethylene content, and the obtained polypropylene alloy material has a low light transmittance and a high haze; in Comparative Examples 5-9, other toughening agents were used instead of the polybutene-1 resin defined by the present invention, and the obtained polypropylene alloy materials cannot simultaneously have a relatively high Charpy impact strength, a high light transmittance and a low haze; in Comparative Example 10, no additional toughening agent was added, and the performance of the obtained material is poor.

[0173] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A polybutene-1 resin, characterized in that, the resin comprises butene-1 structural units and α-olefin structural units; wherein, based on the total weight of the polybutene-1 resin, the content of the α-olefin structural units is 5-11 wt%; wherein, the melt index of the resin at 190 °C and a load of 2.16 kg is 1-2 g / 10 min; wherein, the glass transition temperature of the resin is -30 °C to -44 °C.

2. The resin according to claim 1, wherein, based on the total weight of the polybutene-1 resin, the content of the α-olefin structural units is 6-10 wt%; preferably, the melt index of the resin at 190 °C and a load of 2.16 kg is 1.2-1.7 g / 10 min; preferably, the glass transition temperature of the resin is -35 to -43 °C; preferably, the melting enthalpy of the resin is 15-30 J / g, preferably 16-28 J / g; preferably, the molecular weight distribution (Mw / Mn) of the resin is 4.5-12, preferably 5-9.

3. The resin according to claim 1 or 2, wherein, the α-olefin is selected from ethylene and / or propylene, more preferably ethylene.

4. The resin according to any one of claims 1-3, wherein, the resin further comprises: a main catalyst, a main catalyst, an electron donor and an auxiliary agent; preferably, the main catalyst is a Ziegler-Natta catalyst; preferably, the cocatalyst is an alkyl aluminum, preferably selected from at least one of trimethyl aluminum, triethyl aluminum, triisobutyl aluminum and tri-n-butyl aluminum, more preferably triisobutyl aluminum; preferably, the electron donor is a siloxane external electron donor, preferably selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, methyl tert-butyl dimethoxysilane and cyclohexylmethyldimethoxysilane, more preferably cyclohexylmethyldimethoxysilane; preferably, the mass ratio of the main catalyst, the cocatalyst and the electron donor is 0.01-0.02:0.1-0.75:0.1-0.8; preferably, based on the total weight of the polybutene-1 resin, the total amount of the main catalyst, the cocatalyst and the electron donor is 0.015-0.2 wt%.

5. The resin according to claim 4, wherein, the auxiliary agent comprises an antioxidant and / or an acid scavenger; preferably, the antioxidant is selected from hindered phenol antioxidants and / or phosphite antioxidants, preferably selected from at least one of antioxidant 168, antioxidant 1010, antioxidant 705T and antioxidant 1076; preferably, the acid scavenger is selected from at least one of hydrotalcite, calcium stearate and zinc stearate; preferably, based on the total amount of the polybutene-1 resin, the content of the auxiliary agent is 0.1-1 wt%; preferably, the mass ratio of the antioxidant and the acid scavenger is 0.45-0.65:0.15-0.

4.

6. A method for preparing the polybutene-1 resin according to any one of claims 1-5, wherein, the method comprises: In the presence of a solvent, a main catalyst, a cocatalyst and an electron donor are mixed, and subjected to a polymerization reaction with 1-butene, α-olefins and hydrogen introduced under different pressures, and then an auxiliary agent is added to obtain a polybutene-1 resin; Preferably, the method comprises: mixing a main catalyst suspension, a cocatalyst solution and an electron donor solution, subjecting them to a polymerization reaction with 1-butene, α-olefins and hydrogen introduced under different pressures, and then adding an auxiliary agent, and drying to obtain a polybutene-1 resin.

7. The method according to claim 6, wherein, the solvent is an inert organic solvent, preferably at least one selected from white oil, n-hexane, n-octane, isohexane and heptane, more preferably n-hexane; Preferably, the content of the main catalyst in the main catalyst suspension is 0.5-5 mg / mL, the content of the cocatalyst in the cocatalyst solution is 0.15-0.5 mol / L, and the content of the electron donor in the electron donor solution is 0.5-1.5 mol / L; Preferably, the polymerization reaction comprises two stages: in the first stage, the pressure of the introduced α-olefin is 0.8-2 bar, the pressure of the introduced hydrogen is 0.5-1 bar, and the time of the first stage is 0.5-2.5 h; in the second stage, the pressure of the introduced α-olefin is 0.8-2 bar, the pressure of the introduced hydrogen is 0.5-1 bar, and the time of the second stage is 0.5-2.5 h; the temperature of the polymerization reaction is 70-80 °C.

8. A polypropylene alloy material, characterized in that it comprises the polybutene-1 resin according to any one of claims 1-5 and a polypropylene resin; Preferably, based on the total amount of the polypropylene alloy material, the content of the polybutene-1 resin is 3-7.5 wt%. Preferably, the material has a notched Izod impact strength of 5-8 kJ / m at room temperature (25°C). 2 ; and a notched Izod impact strength of 1.5-2.5 kJ / m at -10°C. 2 ; a flexural modulus of 1150-1400 MPa; a light transmittance of 90-92% for a 1-mm thin sheet; and a haze of 35-45.

9. A method for preparing the polypropylene alloy material according to claim 8, wherein, the method comprises: mixing the polybutene-1 resin and the polypropylene resin, melting, extruding and pelletizing to obtain the polypropylene alloy material; Preferably, the temperature of the extrusion is 180-250 °C.

10. The application of the polypropylene alloy material according to claim 8 or the polypropylene alloy material prepared by the method according to claim 9 in food packaging products or daily necessities.

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