A polybutene-1 alloy and preparation method thereof

Abstract

The invention discloses a polybutene-1 alloy and a preparation method thereof, comprising the following steps: step 1, propylene is subjected to liquid phase bulk polymerization under the action of a catalyst system to obtain polypropylene particles carrying active centers; step 2, the polypropylene particles and butene-1 monomer are subjected to gas phase polymerization to obtain the polybutene-1 alloy. The polybutene-1 alloy produced by the method of the invention has a good spherical morphology, isotacticity ≥ 95%, a molecular weight distribution controllable within 5-10, a Shore hardness controllable within 60-38, is soft plastic, has excellent impact resistance, and does not generate three wastes in a continuous polymerization process, is clean and environmentally friendly, and belongs to the field of green chemistry.

Description

Technical Field

[0001] The invention relates to the field of petrochemical industry, and in particular to a high-impact polybutene-1 alloy and a preparation method thereof. Background Art

[0002] Highly isotactic polybutene-1 is a semi-crystalline polyolefin thermoplastic resin polymerized from butene-1 monomer. It is known as "plastic gold" because of its excellent heat resistance, durability, chemical stability and other characteristics. At present, the production process of polybutene-1 mostly adopts the liquid phase bulk method. Compared with the gas phase method and slurry method, the bulk method polybutene-1 production process has the advantages of simple process, low cost, and good product morphology. However, since polybutene-1 will swell in its monomer when the polymerization temperature is higher than 30°C, it will cause the system to become sticky, thereby affecting mass transfer and heat transfer, resulting in the failure of the polybutene-1 product quality to meet the index requirements. In addition, the performance of polybutene-1 material is related to its isotacticity and crystal transformation. The thermodynamically unstable crystal form II in polybutene-1 is transformed into the stable crystal form I, so that polybutene-1 presents high yield strength and high modulus mechanical properties, but it takes seven to ten days of conversion time at room temperature to complete this crystal transformation, which directly restricts the production and use of polybutene-1.

[0003] In order to solve the problems existing in the production and application of polybutene-1 materials, the method of copolymerizing butene-1 monomer with other α-olefins can be used to synthesize polybutene-1 in-reactor alloy, so that the problems of swelling and stickiness of the polymerization product and poor particle morphology during the polymerization process can be improved. At the same time, without affecting the application performance of polybutene-1, the crystal transformation time of polybutene-1 can be greatly shortened, and it can be endowed with certain specific properties.

[0004] Chinese patent CN103951898 A discloses a method for preparing polybutene-1 / propylene alloy by bulk polymerization, wherein butene-1 is prepolymerized and then propylene or a mixed gas of butene-1 and propylene is introduced to perform in-situ polymerization in two stages to obtain a powdered alloy material mainly composed of polybutene-1 and a small amount of butene-1 / propylene copolymer.

[0005] Basel Polyolefins Company ZL03800736.3 discloses a method for synthesizing 1-butene homopolymer or 1-butene copolymer containing up to 20 wt% of other α-olefins by solution polymerization, wherein the Mw / Mn of the product is less than 6 and the melt strength is greater than 2.8 g.

[0006] CN1140545C of Montel Technology Company discloses the use of solution polymerization to synthesize 1-butene homopolymer or 1-butene copolymer containing up to 20wt% of other α-olefins. The Mw / Mn of the product is greater than 6, which is very suitable for preparing pipes.

[0007] Neste Corporation CN1032172A discloses that a poly-α-olefin catalyst composition is prepared by bulk prepolymerization (liquid phase bulk polymerization), and then butene-1 polymerization (liquid phase bulk polymerization) is carried out on this basis to obtain a polybutene-1 copolymer with high crystallinity.

[0008] The above polymerizations all adopt the solution method to prepare polybutene-1 alloy. Although the problem of product swelling and stickiness is solved to a certain extent, the polymerization product still needs to be separated and the unreacted monomers need to be refined and recovered. The post-processing process is relatively complicated and it is difficult to achieve continuous production. At the same time, the above polymerization process adopts the traditional ZN catalyst system to prepare polybutene-1 alloy, which will affect the melting point, mechanical properties and thermal stability of polybutene-1. Summary of the invention

[0009] The main purpose of the present invention is to provide a polybutene-1 alloy and a preparation method thereof, so as to overcome the defects of the prior art that the post-treatment of the polybutene-1 alloy is complicated and the obtained polybutene-1 alloy has poor performance.

[0010] In order to achieve the above object, the present invention provides a method for preparing a polybutene-1 alloy, comprising the following steps:

[0011] Step 1, propylene is subjected to liquid phase bulk polymerization under the action of a catalyst system to obtain polypropylene particles carrying active centers;

[0012] Step 2: The polypropylene particles and butene-1 monomer are subjected to gas phase polymerization to obtain a polybutene-1 alloy.

[0013] The preparation method of the polybutene-1 alloy of the present invention, wherein the catalyst system comprises a supported ZN catalyst, the supported ZN catalyst comprises a carrier and an active component, the carrier is an inorganic component doped with magnesium chloride, and the inorganic component is selected from NaCl, LiCl, ZnCl 2 、MnCl 2 and AlCl 3 At least one of; the active component is TiCl 4 ; The mass content of the inorganic component in the carrier is 0.1%-50%.

[0014] In the method for preparing the polybutene-1 alloy of the present invention, the supported ZN catalyst further comprises an internal electron donor, and the internal electron donor is selected from at least one of esters, ethers or ether-ester composites.

[0015] The preparation method of the polybutene-1 alloy of the present invention, wherein the active component is calculated as titanium, the mass content of the active component in the supported ZN catalyst is 0.50%-4.50%, and the mass content of the internal electron donor is 0.10%-6.56%.

[0016] The preparation method of the polybutene-1 alloy of the present invention, wherein the catalyst system also includes a co-catalyst and an external electron donor; the co-catalyst is an alkyl aluminum compound, and the external electron donor is selected from at least one of silicon, ethers, amines, and esters; the supported ZN catalyst is calculated based on titanium, the co-catalyst is calculated based on aluminum, and the molar ratio of the supported ZN catalyst to the co-catalyst is 1:10-500; the molar ratio of the external electron donor to the supported ZN catalyst is 1:0.01-60.

[0017] The preparation method of the polybutene-1 alloy of the present invention, wherein the co-catalyst is selected from at least one of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, diisopropylaluminum monochloride and diisobutylaluminum monochloride; the external electron donor is selected from at least one of methylcyclohexyldimethoxysilane, diisobutyldimethoxysilane, methyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, 1,1,1-trifluoropropyl-2-ethylpiperidinyl-dimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, methyl-n-butyl ether, methyl isobutyl ether, methyl tert-butyl ether, methyl isopropyl ether, ethyl-n-butyl ether, ethyl isobutyl ether, ethyl tert-butyl ether and ethyl isopropyl ether.

[0018] The preparation method of the polybutene-1 alloy of the present invention, wherein the internal electron donor is selected from ethyl benzoate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dicyclohexyl phthalate, diisooctyl phthalate, dineopentyl phthalate, (2-methoxy)ethyl benzoate, di(2-methoxy)ethyl phthalate, 4-methyl di-n-butyl phthalate, 4-methyl At least one of diisobutyl phthalate, diisooctyl 4-methylphthalate (MDIOP), dineopentyl 4-methylphthalate, dibutyl 4-bromophthalate, diisobutyl 4-bromophthalate, diisooctyl 4-bromophthalate, dineopentyl 4-bromophthalate, phenethyl ether, ethylene glycol dimethyl ether, 9,9-bis(methylmethoxy)fluorene, and 9,9-bis(benzylcarboxymethyl)fluorene.

[0019] The preparation method of the polybutene-1 alloy of the present invention comprises the following steps: the temperature of the liquid phase bulk polymerization is 25-90°C, the polymerization time is 5-150 min; hydrogen is introduced into the liquid phase bulk polymerization, and the partial pressure of the hydrogen is 0.01-0.50 MPa; the amount of propylene added is 2-50 g / mgTiCl 4 .

[0020] The method for preparing the polybutene-1 alloy of the present invention comprises the following steps: the mass ratio of the butene-1 monomer in step 2 to the propylene in step 1 is 0.1-100:1, the gas phase polymerization temperature is 40-80°C, and the polymerization time is 0.5-14h; hydrogen is also introduced during the gas phase polymerization, and the partial pressure of the hydrogen is 0.01-0.50MPa.

[0021] The method for preparing the polybutene-1 alloy of the present invention further comprises decompressing and gasifying the mixture after the liquid phase bulk polymerization to recover unreacted propylene.

[0022] In order to achieve the above-mentioned purpose, the present invention also provides a polybutene-1 alloy, which is obtained by the preparation method described in any one of claims 1-10, and the polybutene-1 alloy is spherical in shape, has an isotacticity of ≥95%, a molecular weight distribution within 5-10, and a Shore hardness within 60-38.

[0023] Beneficial effects of the present invention:

[0024] 1) The present invention adopts a liquid phase bulk method to prepolymerize polypropylene spherical particles with active centers, and performs gas phase polymerization of butene-1 on this basis, which not only does not cause the problem of swelling and stickiness of the polymerization product, but also does not require post-separation treatment of the polymerization product, simplifies the production process, realizes continuous production, and the alloy in the kettle can effectively shorten the crystal transformation time of polybutene-1, thereby improving the production efficiency of the product.

[0025] 2) By inorganically doping the carrier in the supported ZN catalytic system, the catalyst performance is significantly changed, so that its catalytic efficiency is higher and the distribution of catalytic active centers is wider, thereby achieving the regulation of the isotacticity and molecular weight distribution of the polybutene-1 alloy, so that the synthesized polybutene-1 alloy has an isotacticity of ≥95%, a controllable molecular weight distribution within 5-10, and a controllable Shore hardness within 60-38, showing excellent impact resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 is the X-ray diffraction curve of polybutene-1 obtained by gas phase polymerization in Comparative Example 1;

[0027] Figure 2 This is the X-ray diffraction curve of polybutene-1 obtained by staged polymerization in Example 5 of the present invention;

[0028] Figure 3 The molecular weight and molecular weight distribution curve of polybutene-1 obtained by staged polymerization in Example 5 of the present invention. DETAILED DESCRIPTION

[0029] The following is a detailed description of the embodiments of the present invention. The embodiments are implemented based on the technical solution of the present invention, and detailed implementation methods and processes are given. However, the protection scope of the present invention is not limited to the following embodiments. The experimental methods in the following embodiments where specific conditions are not specified are usually based on conventional conditions.

[0030] The present invention provides a method for preparing a polybutene-1 alloy, comprising the following steps:

[0031] Step 1, propylene is subjected to liquid phase bulk polymerization under the action of a catalyst system to obtain polypropylene particles carrying active centers;

[0032] Step 2: The polypropylene particles and butene-1 monomer are subjected to gas phase polymerization to obtain a polybutene-1 alloy.

[0033] The preparation method of the polybutene-1 alloy of the present invention is a staged polymerization method. Through liquid phase bulk polymerization and gas phase polymerization processes, spherical particle products with good morphology can be generated, simplifying the post-separation process of the polymerization product.

[0034] In one embodiment, the method for preparing the polybutene-1 alloy of the present invention is carried out under anhydrous and oxygen-free conditions, comprising:

[0035] Step 1, catalyzing the polymerization of propylene monomer under the action of a catalyst system to generate polypropylene particles with active centers, and then gasifying the unreacted propylene monomer under reduced pressure to recover and purify the unreacted propylene monomer to obtain polypropylene particles carrying active centers;

[0036] Step 2: Polypropylene particles carrying active centers are subjected to gas phase polymerization with butene-1 monomer to obtain a high impact resistant polybutene alloy.

[0037] In another embodiment, the gas phase polymerization reaction is carried out in a gas phase fluidized bed, polypropylene particles carrying active centers enter the gas phase fluidized bed through the catalyst feed port, and butene-1 monomer enters the gas phase fluidized bed through the bottom of the kettle to carry out gas phase polymerization.

[0038] In one embodiment, a molecular weight regulator is further added in step 1, and the molecular weight regulator is hydrogen.

[0039] In one embodiment, the catalyst system includes a supported ZN catalyst, wherein the supported ZN catalyst includes a carrier and an active component, wherein the carrier is an inorganic component doped with magnesium chloride, and the inorganic component is selected from NaCl, LiCl, ZnCl2 、MnCl 2 and AlCl 3 At least one of; the active component is TiCl 4 ; The mass content of the inorganic component in the carrier is 0.1%-50%.

[0040] The present invention forms a doped supported ZN catalyst by doping an inorganic component in a carrier, so that the polymerization product can have a higher isotacticity and a wider molecular weight distribution, thereby making the polymerization product have high impact resistance.

[0041] In one embodiment, the supported ZN catalyst further comprises an internal electron donor, which is a modifier. In another embodiment, the internal electron donor is selected from at least one of esters, ethers or ether-ester composites, for example, ethyl benzoate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dicyclohexyl phthalate, diisooctyl phthalate, dineopentyl phthalate, (2-methoxy)ethyl benzoate, di(2-methoxy)ethyl phthalate, di-n-butyl 4-methylphthalate, 4-(2-methyl)-1-butyl phthalate, di-n-butyl 4-methyl ... -Diisobutyl methyl phthalate, diisooctyl 4-methyl phthalate, dineopentyl 4-methyl phthalate, dibutyl 4-bromophthalate, diisobutyl 4-bromophthalate, diisooctyl 4-bromophthalate, dineopentyl 4-bromophthalate, phenethyl ether, ethylene glycol dimethyl ether, 9,9-di(methylmethoxy)fluorene, 9,9-bis(benzylcarboxymethyl)fluorene, or a mixture of two or more thereof.

[0042] In one embodiment, the active component is calculated as titanium, and in the supported ZN catalyst, the mass content of the active component is 0.50%-4.50%, and the mass content of the internal electron donor is 0.10%-6.56%.

[0043] In one embodiment, the catalyst system further includes a co-catalyst and an external electron donor; the co-catalyst is an alkyl aluminum compound, and the external electron donor is selected from at least one of silicon, ethers, amines, and esters; the supported ZN catalyst is calculated based on titanium, the co-catalyst is calculated based on aluminum, and the molar ratio of the supported ZN catalyst to the co-catalyst is 1:10-500; the molar ratio of the external electron donor to the supported ZN catalyst is 1:0.01-60.

[0044] In another embodiment, the co-catalyst is one or a mixture of two or more of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, diisopropylaluminum monochloride and diisobutylaluminum monochloride; the external electron donor is preferably alkoxysilicon and ether, specifically one or more of methylcyclohexyldimethoxysilane, diisobutyldimethoxysilane, methyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, 1,1,1-trifluoropropyl-2-ethylpiperidinyl-dimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, methyl-n-butyl ether, methyl isobutyl ether, methyl tert-butyl ether, methyl isopropyl ether, ethyl-n-butyl ether, ethyl isobutyl ether, ethyl tert-butyl ether and ethyl isopropyl ether.

[0045] In one embodiment, the temperature of the liquid phase bulk polymerization is 25-90°C, the polymerization time is 5-150 min; the partial pressure of hydrogen in the liquid phase bulk polymerization is 0.01-0.50 MPa; the amount of propylene added is 2-50 g / mgTiCl 4 .

[0046] In one embodiment, the mass ratio of the butene-1 monomer in step 2 to the propylene in step 1 is 0.1-100:1, the gas phase polymerization temperature is 40-80°C, the polymerization time is 0.5-14h; and the partial pressure of hydrogen in the gas phase polymerization is 0.01-0.50MPa.

[0047] The segmented polymerization process of the invention can realize the continuous production of polybutene-1 alloy, and no three wastes are generated during the polymerization process, which is clean and environmentally friendly. The obtained polybutene-1 alloy is in a spherical form, has an isotacticity of ≥95%, a molecular weight distribution controllable within 5-10, a Shore hardness controllable within 60-38, is soft plastic, and has excellent impact resistance.

[0048] The present invention is described in detail below through specific examples, but the use and purpose of these exemplary implementation modes are only used to illustrate the present invention, and do not constitute any form of limitation on the actual protection scope of the present invention, nor limit the protection scope of the present invention to them.

[0049] Test method or test standard:

[0050] The isotacticity is determined by the weight percentage of insoluble matter after ether extraction;

[0051] Gas-gel permeation chromatography was used to determine molecular weight and molecular weight distribution;

[0052] X-ray diffractometer is used to determine the crystal structure of the product;

[0053] Determine the sample density according to GB / T1033-1986;

[0054] Determine the Shore hardness according to GB / T 2411-1989;

[0055] The impact strength was determined according to GB / T1843-2008.

[0056] Example 1

[0057] 1) Preparation of polypropylene active particles

[0058] Under Ar protection, petroleum ether, anhydrous magnesium chloride and ethanol were added into a reactor equipped with a mechanical stirrer, heated to 130 °C and reacted for 2 hours. After the reaction, MgCl was vacuum dried to obtain 2 -EtOH complex, take 20 g MgCl 2 The LiCl-doped carrier was prepared by ball milling a certain amount of LiCl with a certain amount of EtOH complex in a ball mill for a certain period of time. The LiCl-doped carrier was added dropwise to a TiCl solution maintained at -10°C within 2 hours. 4 After the mixture was added to the solution, the temperature was kept at -10 °C for 0.5 hours, then slowly heated to 110 °C for 2 hours, and the reaction mixture was filtered while hot to obtain a solid intermediate product, which was then added to a certain amount of TiCl 4 An internal electron donor is added to the solution at 100°C, and the temperature is raised to 110°C for reaction for 2 hours. The reaction mixture is filtered while hot and washed thoroughly with n-hexane at 60°C until no precipitated titanium compound is detected in the washing liquid, thereby obtaining a solid titanium catalyst, i.e., a supported ZN catalyst.

[0059] The supported ZN catalyst prepared above includes MgCl 2 -LiCl spherical carrier, LiCl accounts for 5% of the carrier's mass content, TiCl 4 As the active center, phthalic acid di (2-methoxy) ethyl ester (PBMOE) is used as the internal electron donor, the titanium content is 2.8%, and the PBMOE content is 3.8%. The 10L stainless steel stirring kettle is heated to 100-120℃, replaced with high-purity nitrogen 3-5 times, and vacuumed to remove all air and water vapor in the kettle. Then the system is cooled to 60℃, and H is filled into the reactor. 2When the pressure gauge pressure reaches 0.1 MPa, 120 g of propylene monomer is charged, and 0.25 mmol cyclohexylmethyldimethoxysilane (CHMMS), 5.0 mmol triethylaluminum and 0.025 mmol of the above-mentioned supported titanium catalyst (in terms of Ti amount) are added through the catalyst feed port. The reaction system is kept at a constant temperature of 50°C for 30 min. During the reaction process, the pressure in the autoclave is constant at 1.5 MPa. After the reaction is completed, the reduced pressure propylene gas is recovered and refined through a recovery pipeline for recycling. The obtained polypropylene active particles are transported to a gas phase fluidized bed reactor through a pipeline.

[0060] 2) Preparation of polybutene-1 alloy

[0061] The polypropylene active particles were transported to an 80L gas phase fluidized bed reactor through a pipeline, and the hydrogen-containing butene-1 monomer was fed into the polymerization reactor at a flow rate of 30L / h through a metering pump. The total feed amount of butene-1 monomer was calculated to be 500g, the hydrogen partial pressure in the reactor was 0.1MPa, the reaction temperature was 45°C, the residence time was 2.5h, and the unreacted monomer and hydrogen were compressed by circulation to achieve continuous production. The isotacticity, density, molecular weight, molecular weight distribution, Shore hardness and impact strength of the polymerized product were measured as shown in Table 2.

[0062] The polymerization and characterization methods of Examples 2 to 14 are the same as those of Example 1. The substances added during the specific polymerization process and the amounts added are shown in Table 1, and the product characterization results are shown in Table 2.

[0063] Table 1 Polymerization materials and polymerization conditions of Examples 2-14

[0064]

[0065]

[0066] Comparative Example 1

[0067] The supported titanium catalyst is MgCl 2 -ZnCl 2 Spherical support, TiCl 4The catalyst comprises a catalyst containing 2-(2-methoxy)ethyl phthalate and ethylene glycol dimethyl ether as the active center, 2-(2-methoxy)ethyl phthalate and ethylene glycol dimethyl ether as the internal electron donor, the molar ratio of 2-(2-methoxy)ethyl phthalate to ethylene glycol dimethyl ether is 2:1, the titanium content in the catalyst is 2.8%, and the internal electron donor content is 3.8%. 0.25mmol cyclohexylmethyldimethoxysilane (CHMMS), 5.0mmol triethylaluminum and 0.025mmol of the above-mentioned supported titanium catalyst (in terms of Ti content) are added to the gas phase fluidized bed through the catalyst feed port. The hydrogen-containing butene-1 monomer is fed into the polymerization reactor at a flow rate of 30L / h through a metering pump. The total feed amount of butene-1 monomer is calculated to be 500g, the hydrogen partial pressure in the kettle is 0.1MPa, the reaction temperature is 45°C, the residence time is 2.5h, and the unreacted monomer and hydrogen are compressed through circulation to achieve continuous production. The isotacticity, density, molecular weight, molecular weight distribution, Shore hardness and impact strength of the polymerized product are shown in Table 2. The X-ray diffraction spectra of the polybutene-1 product of Comparative Example 1 and Example 5 are shown in Table 2. Figure 1 and 2 shown.

[0068] Table 2 Characterization results of polybutene-1 products

[0069]

[0070] The above results show that the isotacticity of the polybutene-1 alloy prepared by the liquid phase bulk and gas phase staged polymerization method is ≥95%. The molecular weight distribution of the polybutene-1 alloy can be controlled within 5-10 and the Shore hardness can be controlled within 60-38 by using the doped supported ZN catalyst system. The product has excellent impact resistance. 2 When the internal electron donor is a composite of inorganic dopant, di(2-methoxy)ethyl phthalate, and ethylene glycol dimethyl ether, the impact strength of the polybutene-1 alloy is as high as 32.4 MPa. Figure 1 and Figure 2 From the X-ray diffraction curve, it can be seen that after the polymer is melted, diffraction peaks of polybutene crystal form II appear at 2θ=11.6°, 16.5° and 18.0°, and diffraction peaks of polybutene crystal form I appear at 2θ=9.8°, 17.1° and 20.2°. And as the time of the melted polymer being placed at room temperature increases, the diffraction peak of crystal form II becomes significantly weaker, while the diffraction peak of crystal form I becomes significantly stronger. This further proves that crystal form I is a stable crystal form. Figure 2 It can also be seen that after the segmented polybutene-1 is melted, the diffraction peak of Form II rapidly weakens, while the characteristic diffraction peak of Form I rapidly strengthens. After being placed at room temperature for 168 hours, the diffraction peak of Form II almost disappears, while Figure 1The XRD spectrum of the characterized polybutene-1 without segmented polymerization still showed the diffraction peak of Form II within the experimental time of 240 hours, indicating that the time for the polybutene-1 obtained by segmented polymerization to transform from the metastable Form II to the stable Form I is shortened.

[0071] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, technicians familiar with the field may make various corresponding changes and deformations based on the present invention, but these corresponding changes and deformations should all fall within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing a polybutene-1 alloy, characterized in that: The steps include: Step 1, propylene is subjected to liquid phase bulk polymerization under the action of a catalyst system to obtain polypropylene particles carrying active centers; Step 2, the polypropylene particles and butene-1 monomer are subjected to gas phase polymerization to obtain a polybutene-1 alloy; Wherein, the catalyst system comprises a supported ZN catalyst, the supported ZN catalyst comprises a carrier and an active component, the carrier is magnesium chloride doped with an inorganic component, the inorganic component is selected from at least one of NaCl, LiCl, ZnCl2, MnCl2 and AlCl3, and the mass content of the inorganic component in the carrier is 0.1%-50%; the active component is TiCl4; Wherein, the gas phase polymerization reaction is carried out in a gas phase fluidized bed.

2. The method for preparing the polybutene-1 alloy according to claim 1, characterized in that: The supported ZN catalyst further comprises an internal electron donor, and the internal electron donor is selected from at least one of esters, ethers and ether-ester composites.

3. The method for preparing the polybutene-1 alloy according to claim 2, characterized in that: The active component is calculated on the basis of titanium. In the supported ZN catalyst, the mass content of the active component is 0.50%-4.50%, and the mass content of the internal electron donor is 0.10%-6.56%.

4. The method for preparing the polybutene-1 alloy according to claim 1, characterized in that: The catalyst system also includes a co-catalyst and an external electron donor; the co-catalyst is an alkyl aluminum compound, and the external electron donor is selected from at least one of silicon, ethers, amines, and esters; the supported ZN catalyst is calculated based on titanium, the co-catalyst is calculated based on aluminum, and the molar ratio of the supported ZN catalyst to the co-catalyst is 1:10-500; the molar ratio of the external electron donor to the supported ZN catalyst is 1:0.01-60.

5. The method for preparing the polybutene-1 alloy according to claim 4, characterized in that: The co-catalyst is selected from at least one of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, diisopropylaluminum monochloride and diisobutylaluminum monochloride; the external electron donor is selected from at least one of methylcyclohexyldimethoxysilane, diisobutyldimethoxysilane, methyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, 1,1,1-trifluoropropyl-2-ethylpiperidinyl-dimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, methyl-n-butyl ether, methyl isobutyl ether, methyl tert-butyl ether, methyl isopropyl ether, ethyl-n-butyl ether, ethyl isobutyl ether, ethyl tert-butyl ether and ethyl isopropyl ether.

6. The method for preparing the polybutene-1 alloy according to claim 2, characterized in that: The internal electron donor is selected from ethyl benzoate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dicyclohexyl phthalate, diisooctyl phthalate, dineopentyl phthalate, (2-methoxy)ethyl benzoate, di(2-methoxy)ethyl phthalate, di-n-butyl 4-methylphthalate, diisobutyl 4-methylphthalate, diisooctyl 4-methylphthalate (MDIOP), dineopentyl 4-methylphthalate, dibutyl 4-bromophthalate, diisobutyl 4-bromophthalate, diisooctyl 4-bromophthalate, dineopentyl 4-bromophthalate, ethyl ether, ethylene glycol dimethyl ether, 9,9-di(methylmethoxy)fluorene, 9 , at least one of 9-bis(benzylcarboxymethyl)fluorene.

7. The method for preparing the polybutene-1 alloy according to claim 1, characterized in that: The temperature of the liquid phase bulk polymerization is 25-90°C, and the polymerization time is 5-150min. Hydrogen is also introduced into the liquid phase bulk polymerization, and the partial pressure of the hydrogen is 0.01-0.50MPa. The amount of propylene added is 2-50g / mgTiCl4.

8. The method for preparing the polybutene-1 alloy according to claim 1, characterized in that: The mass ratio of the butene-1 monomer in step 2 to the propylene in step 1 is 0.1-100:1, the gas phase polymerization temperature is 40-80°C, and the polymerization time is 0.5-14h; hydrogen is also introduced into the gas phase polymerization, and the partial pressure of the hydrogen is 0.01-0.50MPa.

9. The method for preparing a polybutene-1 alloy according to claim 1, characterized in that: The method also includes decompressing and gasifying the mixture after the liquid phase bulk polymerization to recover unreacted propylene.

Images