CN115894751B - 1-butene polymerization catalyst and preparation method and application thereof - Google Patents

1-butene polymerization catalyst and preparation method and application thereof Download PDF

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CN115894751B
CN115894751B CN202310036623.3A CN202310036623A CN115894751B CN 115894751 B CN115894751 B CN 115894751B CN 202310036623 A CN202310036623 A CN 202310036623A CN 115894751 B CN115894751 B CN 115894751B
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compound
butene
titanium
catalyst
polymerization catalyst
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CN115894751A (en
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安振永
曹坚
任合刚
高晶杰
刘汉英
董月梅
逯云峰
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Beijing Petrochemical Engineering Co Ltd
Guangdong University of Petrochemical Technology
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Beijing Petrochemical Engineering Co Ltd
Guangdong University of Petrochemical Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention provides a 1-butene polymerization catalyst, a preparation method and application thereof. The catalyst comprises: the magnesium halide support, and titanium compound with Ti-halogen bond and built-in electron donor compound loaded on the support, wherein the built-in electron donor compound comprises a combination of phthalate compound, 1, 3-diether compound and succinate compound. The preparation method of the catalyst comprises the following steps: the magnesium halide carrier, the titanium compound with Ti-halogen bond, the nonionic surfactant and the compound internal electron donor compound are contacted and reacted in an inert solvent to obtain the 1-butene polymerization catalyst. The invention also provides application of the catalyst in homo-polymerization or copolymerization of 1-butene. The polybutene-1 resin with high isotacticity and adjustable molecular weight and molecular weight distribution can be prepared by adopting the 1-butene polymerization catalyst.

Description

1-butene polymerization catalyst and preparation method and application thereof
Technical Field
The invention relates to a 1-butene polymerization catalyst, a preparation method and application thereof, and belongs to the technical field of polymerization catalysts.
Background
Polybutene-1 is prepared by polymerizing 1-butene monomer as material in the presence of catalyst in bulk, solution or slurry process. It is a semi-crystalline polyolefin thermoplastic resin with good mechanical properties; outstanding environmental stress crack resistance and heat resistance; excellent creep resistance, repeated winding and continuous, and good creep resistance even at elevated temperatures; good resistance to chemical attack; abrasion resistance similar to ultra high molecular weight polyethylene; high filler filling properties, etc. Therefore, the polybutene-1 can be used for producing pipelines, films, plates, various containers and the like, and is particularly suitable for being used as a floor heating pipe.
It is known that since the advent of Ziegler-Natta catalysts, the catalytic activity has been increased from tens of times of the previous first generation to tens of thousands times at present, the isotacticity of the polymerization product has been able to be more than 98%, and the production process has been simplified. Wherein, mgCl 2 The carrier type Ziegler-Natta catalyst is an important catalyst for preparing polyolefin, wherein an electron donor plays a key role, and finding an ideal electron donor compound is always a hot spot for Ziegler-Natta catalyst synthesis research.
TiCl is employed in EP0201647A1 4 /DNBP/Mg(C 2 H 5 O) 2 -AlEt 3 The catalyst system of the/phenyl triethoxysilane catalyzes the polymerization of the butene-1, the polymerization activity is at most 2667gPB/g Cat.3.8 h, namely 701gPB/g Cat.h, and the bulk density of the polybutene-1 is 0.30g/cm 3 . Although this production method gives polybutene-1 in the form of pellets, its polymerization activity is too low, and a step of separating the catalyst residues is required so as not to deteriorate the physical properties of the produced polymer. TiCl is used in U.S. Pat. No. 3,379,B1 (CN 1256698A) 4 DNBP/spherical magnesium chloride (MgCl) 2 ·2.1C 2 H 5 OH)-AlEt 3 (or Al) i Bu 3 ) The catalyst system of diisopropyl dimethoxy silane (DIPMS) takes butene-1 as a solvent and a reaction monomer to prepare the high stereospecific polybutene-1 with the isotacticity higher than 95 percent, the ppm content of titanium in the polymer is lower than 50, the molecular weight distribution is more than or equal to 6, and the catalytic activity is 3500g/g Cat.h. However, the catalytic activity of this process is still far lower than those of the efficient polyethylene and polypropylene polymers, and the productivity of the process is therefore low. US7345122bB2 (CN 1590417 a) uses TiCl 4 1, 3-diether/anhydrous magnesium chloride/isooctanol-AlEt containing silicon atoms 3 (or Al) i Bu 3 ) And/silane external electron donor (such as DPMS and DIBDMS) catalytic system, polybutene-1 with isotacticity higher than 98% is obtained, polymerization activity is 9800-20000 gPB/g Cat.h, and polymer molecular weight distribution is 4-6. Although the preparation method has higher catalytic activity and polymer isotacticity, and can meet the commercial production in large batch, the polymer has narrower molecular weight distribution, which is not beneficial to the development of more brands of products. CN1374327A employs TiCl 4 2-isopropyl-2-isobutyl-1, 3-dimethoxypropane (or diisobutyl phthalate)/anhydrous magnesium chloride/isooctanol-AlEt 3 (or Al) i Bu 3 ) And/silane external electron donor (such as DPMS and DIBDMS) catalytic system to obtain polybutene-1 copolymer with isotacticity of 91-95%, polymerization activity of 4800g/g Cat.h and polymer molecular weight distribution of 3.5-4.6. It can be seen that the catalyst has lower activity and narrower molecular weight distribution of the polymer, which is unfavorable for improving the production efficiency and developing more brands of products.
CN101020728A reports a bulk precipitation synthesis method of high isotactic polybutene-1, in which a catalyst composed of magnesium halide supported titanium compound-organic aluminum compound prepared by grinding method is used to initiate polymerization of 1-butene (such as TiCl) 4 9, 9-bis (methoxymethyl) fluorene/MgCl 2 -AlEt 3 According to the DDS catalytic system), the particle morphology of the catalyst is irregular, and the obtained polybutene-1 is very irregular in particle morphology and extremely easy to adhere, so that mass transfer and heat transfer are difficult. CN104193870A reports a catalyst for improving isotacticity of polybutene-1 and accelerating crystal form conversion of polybutene-1The catalyst is composed of titanium compound-alkyl aluminum-external electron donor loaded by carrier, diisobutyl phthalate is used as internal electron donor and methylcyclohexyl dimethoxy silane is used as external electron donor, and the isotacticity of polybutene-1 is up to 95.8%. CN106554442a reports the synthesis of polybutene-1 using organosilane as external donor, ziegler-natta catalysts of N-series, DQ-series and TK-260-series, improving the catalyst particle strength by propylene prepolymerization in order to achieve the effect of reducing the content of low molecular weight products, but its polybutene-1 isotacticity is only 95.1%. CN103288993a discloses a catalyst for high isotacticity polybutene-1, polybutene with isotacticity greater than 95% is prepared, and its catalytic efficiency is not greater than 440Kg polybutene-1/gTi. CN103304709B reports a solid catalyst for polymerization of 1-butene, the composition of the main catalyst comprises magnesium halide, titanium halide and internal electron donor, different substituted 5-norbornene compounds are adopted as internal electron donor, when the catalyst is used for polymerization of 1-butene, the catalyst activity is up to 27.0KgPB/gTi, the isotacticity of the polymer is up to 95.2%, and the molecular weight distribution is up to 11.4.CN111269341a reports a catalyst for synthesizing high isotactic polybutene-1 and a preparation method thereof, spherical magnesium chloride is adopted to load titanium tetrachloride/an electron donor, the electron donor is esters or diethers, when the catalyst is used for polymerizing 1-butene, the catalytic efficiency reaches 1200Kg polymer/g titanium, the isotacticity of polybutene-1 is more than 98%, and the polymer particle shape is good.
As can be seen from the prior art, the electron donors used in Ziegler-Natta catalysts are esters of phthalic acid such as ethyl benzoate monoester and diisobutyl phthalate, or one or two of 1, 3-diethers such as 2-isopropyl-2-isobutyl-1, 3-dimethoxypropane. Although the activity of the diester electron donor is inferior to that of diethers, the diester electron donor makes the molecular weight distribution of the prepared polymer wider, which is beneficial to improving the processability of the product; although the diether electron donor has high activity and strong orientation capability, the molecular weight distribution of the prepared polymer is narrower, which is not beneficial to the processing of products and the development of more product brands.
Therefore, the development of a novel 1-butene polymerization catalyst and a preparation method thereof are still one of the problems to be solved in the art.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a 1-butene polymerization catalyst and a preparation method and application thereof. The 1-butene polymerization catalyst provided by the invention has the advantages of good sphericity, high catalytic activity and the like. The polybutene-1 resin with high isotacticity and adjustable molecular weight and molecular weight distribution can be prepared by adopting the 1-butene polymerization catalyst.
In order to achieve the above object, the first aspect of the present invention provides a 1-butene polymerization catalyst comprising: a magnesium halide carrier, and a titanium compound with Ti-halogen bond and a compound internal electron donor compound loaded on the carrier, wherein the compound internal electron donor compound comprises a combination of phthalate compound, 1, 3-diether compound and succinate compound; wherein, based on the total weight of the 1-butene polymerization catalyst being 100%, the weight percentage of Ti is 1.8-7.0%, the weight percentage of the compound internal electron donor compound is 1.0-12.0%, and the balance is the magnesium halide carrier.
In the above-mentioned 1-butene polymerization catalyst, preferably, the molar ratio of the phthalate compound, the 1, 3-diether compound and the succinate compound is 1: (0.1-0.5): (0.2-0.8).
In the above-mentioned 1-butene polymerization catalyst, preferably, the phthalate compound comprises one or a combination of several of dibutyl phthalate (DNBP), diisobutyl phthalate (DIBP), dicyclohexyl phthalate (DCHP), diisooctyl phthalate (DIOP), and dipentamyl phthalate (DPP), etc.
In the above-mentioned 1-butene polymerization catalyst, preferably, the 1, 3-diether compound comprises one or a combination of several of 2, 2-diisopropyl-1, 3-dimethoxypropane (dipdpmop), 2-diisobutyl-1, 3-dimethoxypropane (dibdpop), 2-diphenyl-1, 3-dimethoxypropane (DPDMOP) and the like.
In the above-mentioned 1-butene polymerization catalyst, preferably, the succinic acid ester compound includes one or a combination of several of diethyl 2, 3-diisopropylsuccinate (DIPSDE), diethyl 2, 3-diisobutylsuccinate (DIBSDE), dimethyl 2, 3-diisopropylsuccinate (DIPSDM), dimethyl 2, 3-diisobutylsuccinate (DIBSDM), and the like.
In the above-mentioned 1-butene polymerization catalyst, preferably, the titanium compound having a Ti-halogen bond includes one or a combination of several of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium trichloroethoxy, titanium methoxytrichloride, titanium propoxytrichloride, titanium n-butoxytrichloride, titanium dimethoxy dichloride, titanium dichloro diethoxide, titanium dipropoxy dichloride, titanium di-n-butoxy dichloride, titanium trimethoxychloride, titanium triethoxy chloride, titanium tripropoxy chloride, titanium tri-n-butoxy chloride and the like. More preferably, the titanium compound is titanium tetrachloride.
In the above-mentioned catalyst for polymerization of 1-butene, preferably, the magnesium halide support is prepared by: under the protection of inert gas, mixing magnesium dihalide and organic alcohol in an inert solvent, reacting for a period of time at a proper temperature, then cooling the system to the proper temperature, adding halogenated hydrocarbon into the system, and reacting for a period of time to obtain a mixed system containing a magnesium halide carrier.
In the above-mentioned catalyst for polymerization of 1-butene, preferably, in the step of preparing the magnesium halide support, the magnesium dihalide comprises one or a combination of several of magnesium chloride, magnesium bromide, magnesium iodide and the like. More preferably, the magnesium dihalide is magnesium chloride (preferably anhydrous magnesium chloride).
In the above-mentioned catalyst for polymerizing 1-butene, preferably, in the step of preparing the magnesium halide support, the organic alcohol comprises one or a combination of several of the organic alcohols of C2 to C8. More preferably, the organic alcohol comprises one or a combination of several of ethanol, propanol, n-butanol, isobutanol, n-hexanol, n-octanol, isooctanol and the like. Further preferably, the organic alcohol is isooctyl alcohol.
In the above-mentioned 1-butene polymerization catalyst, preferably, in the preparation step of the magnesium halide support, the molar ratio of the organic alcohol to the magnesium dihalide is (2.0 to 4.0): 1.
In the above-mentioned catalyst for polymerization of 1-butene, preferably, in the step of preparing the magnesium halide support, the halogenated hydrocarbon comprises one or a combination of several of 1-chloroethane, 1-chloropropane, 1-chlorobutane, 1-chlorohexane and the like. More preferably, the halogenated hydrocarbon is 1-chlorobutane.
In the above-mentioned 1-butene polymerization catalyst, preferably, in the preparation step of the magnesium halide support, the mass ratio of the halogenated hydrocarbon to the magnesium dihalide is (2.5 to 4): 1.
in the above-mentioned catalyst for polymerizing 1-butene, preferably, in the preparation step of the magnesium halide support, after mixing magnesium dihalide and an organic alcohol in an inert solvent, the mixture is reacted at 110 to 135℃for 1 to 4 hours.
In the above-mentioned catalyst for polymerizing 1-butene, preferably, in the preparation step of the magnesium halide support, the system is cooled to 50 to 70 ℃, halogenated hydrocarbon is added thereto, and the reaction is carried out for 0.5 to 1 hour.
In the above-mentioned 1-butene polymerization catalyst, preferably, in the preparation step of the magnesium halide support, the inert gas may include high-purity nitrogen gas.
In the above-mentioned 1-butene polymerization catalyst, preferably, in the preparation step of the magnesium halide support, the inert solvent includes one or a combination of several of alkane solvents, and a conventional inert alkane solvent such as, but not limited to, n-decane and the like may be employed. More preferably, the inert solvent may be used in an amount of 20 to 50mL/g magnesium dihalide.
In the above-mentioned catalyst for polymerization of 1-butene, the preparation step of the magnesium halide support may be carried out under stirring conditions, and the rotation speed of stirring may be adjusted conventionally by those skilled in the art according to practical circumstances.
In the above-mentioned catalyst for polymerization of 1-butene, after the preparation step of the magnesium halide support is carried out to obtain a mixed system containing the magnesium halide support, conventional operations such as rapid cooling of the system can be optionally carried out to solidify the particles, thereby obtaining a solid magnesium halide support. The mixed system containing the magnesium halide carrier can be directly used for the subsequent preparation of the catalyst without a curing step.
According to a specific embodiment of the present invention, preferably, the 1-butene polymerization catalyst is prepared by the steps of: the magnesium halide carrier, the titanium compound with Ti-halogen bond, the nonionic surfactant and the compound internal electron donor compound are contacted and reacted in an inert solvent to obtain the 1-butene polymerization catalyst.
More preferably, the 1-butene polymerization catalyst is prepared by the steps of:
s1, adding a magnesium halide carrier into a mixed solution of a titanium compound with Ti-halogen bond and an inert solvent, adding a nonionic surfactant, then keeping the temperature at-10 to 25 ℃ for 0.5 to 1 hour, heating to 105 to 120 ℃ and keeping the temperature for 1 to 3 hours, and carrying out solid-liquid separation to obtain a first solid product;
S2, adding the first solid product into a mixed solution of a titanium compound with Ti-halogen bond and an inert solvent, adding a compound internal electron donor compound at 50-80 ℃, heating to 90-110 ℃ and keeping for 1-3 hours, and then at least carrying out solid-liquid separation to obtain the 1-butene polymerization catalyst.
Among them, it is preferable that in step S1, the mixed system containing the magnesium halide support (obtained by the above-mentioned preparation step of the magnesium halide support) is dropwise added to a mixed solution of a titanium compound having a Ti-halogen bond and an inert solvent, which is maintained at a temperature of 0 ℃. The dripping can be performed within 1.5-2.5 hours by adopting a peristaltic pump.
Wherein, preferably, in step S1, the inert solvent includes one or a combination of several of alkane solvents and aromatic hydrocarbon solvents, etc., such as, but not limited to, toluene, etc. More preferably, the mass ratio of the inert solvent to the magnesium halide support in step S1 is (12 to 18): 1.
wherein, preferably, in the step S1, the mass ratio of the titanium compound having Ti-halogen bond to the magnesium halide support is (25-32): 1.
wherein, preferably, in step S1, the nonionic surfactant includes one or a combination of several of polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene ether, polymethacrylate, and the like. More preferably, the nonionic surfactant is a polymethacrylate.
Wherein, preferably, in step S1, the dosage ratio of the nonionic surfactant to the magnesium halide support is (0.1-0.3) mL:1g.
Preferably, in step S1, the temperature is raised to 105 to 120 ℃ within 6 hours and maintained for 1 to 3 hours.
In step S1, the solid-liquid separation may be preferably performed by hot filtration.
Wherein, preferably, in step S2, the inert solvent includes one or a combination of several of alkane solvents and aromatic hydrocarbon solvents, etc., such as, but not limited to, toluene, etc. More preferably, the mass ratio of the inert solvent to the first solid product in step S2 is (12 to 18): 1.
wherein, preferably, in step S2, the mass ratio of the titanium compound having a Ti-halogen bond to the first solid product is (25 to 32): 1.
wherein, preferably, in step S2, 0.05 to 0.6mol of the built-in internal electron donor compound is added per mol of Mg, based on the amount of Mg in the magnesium halide support.
In step S2, the solid-liquid separation may be preferably performed by hot filtration. After solid-liquid separation, washing and other steps may be performed to obtain the 1-butene polymerization catalyst. Preferably, the washing process may specifically be: and (3) washing the second solid product obtained after the solid-liquid separation in the step (S2) for 1-3 times by adopting toluene at 80-100 ℃, and then fully washing by adopting normal hexane at 50-70 ℃ until no precipitated titanium compound is detected in the cleaning liquid, thereby obtaining the 1-butene polymerization catalyst.
According to a specific embodiment of the present invention, it is preferable that the average particle diameter of the 1-butene polymerization catalyst is 40 to 70 μm.
The invention provides a 1-butene polymerization catalyst, which comprises a magnesium halide carrier, a titanium compound with Ti-halogen bond and a compound internal electron donor compound as a modifier, wherein the titanium compound is loaded on the carrier, the compound internal electron donor compound is used as a modifier, and a nonionic surfactant is added in the preparation process as a morphology control agent. The catalyst creatively adopts three compounds of phthalate compounds, 1, 3-diether compounds and succinate compounds as internal electron donors, avoids the defects of three internal electron donors of diethers, diesters and succinates, fully exerts the respective advantages thereof, and combines the carrier and titanium compounds of the invention, thereby leading the catalyst to have the advantages of high catalytic activity, high directionality, excellent copolymerization performance, good hydrogen regulation and the like. The polybutene-1 resin with high isotacticity and adjustable molecular weight and molecular weight distribution can be prepared by adopting the 1-butene polymerization catalyst.
The second aspect of the invention provides a preparation method of the 1-butene polymerization catalyst, which comprises the following steps:
s1, adding a magnesium halide carrier into a mixed solution of a titanium compound with Ti-halogen bond and an inert solvent, adding a nonionic surfactant, then keeping the temperature at-10 to 25 ℃ for 0.5 to 1 hour, heating to 105 to 120 ℃ and keeping the temperature for 1 to 3 hours, and carrying out solid-liquid separation to obtain a first solid product;
s2, adding the first solid product into a mixed solution of a titanium compound with Ti-halogen bond and an inert solvent, adding a compound internal electron donor compound at 50-80 ℃, heating to 90-110 ℃ and keeping for 1-3 hours, and then at least carrying out solid-liquid separation to obtain the 1-butene polymerization catalyst.
In the above preparation method, preferably, the magnesium halide support is prepared by: under the protection of inert gas, mixing magnesium dihalide and organic alcohol in an inert solvent, reacting for a period of time at a proper temperature, then cooling the system to the proper temperature, adding halogenated hydrocarbon into the system, and reacting for a period of time to obtain a mixed system containing a magnesium halide carrier.
In the above-mentioned production method, preferably, in the production step of the magnesium halide support, the magnesium dihalide includes one or a combination of several of magnesium chloride, magnesium bromide, magnesium iodide and the like. More preferably, the magnesium dihalide is magnesium chloride (preferably anhydrous magnesium chloride).
In the above-mentioned production method, preferably, in the production step of the magnesium halide support, the organic alcohol includes one or a combination of several of the organic alcohols of C2 to C8. More preferably, the organic alcohol comprises one or a combination of several of ethanol, propanol, n-butanol, isobutanol, n-hexanol, n-octanol, isooctanol and the like. Further preferably, the organic alcohol is isooctyl alcohol.
In the above-mentioned production method, preferably, in the production step of the magnesium halide support, the molar ratio of the organic alcohol to the magnesium dihalide is (2.0 to 4.0): 1.
in the above-mentioned production method, preferably, in the production step of the magnesium halide support, the halogenated hydrocarbon includes one or a combination of several of 1-chloroethane, 1-chloropropane, 1-chlorobutane, 1-chlorohexane and the like. More preferably, the halogenated hydrocarbon is 1-chlorobutane.
In the above-mentioned production method, preferably, in the production step of the magnesium halide support, the mass ratio of the halogenated hydrocarbon to the magnesium dihalide is (2.5 to 4): 1.
in the above preparation method, preferably, in the preparation step of the magnesium halide support, after mixing magnesium dihalide and organic alcohol in an inert solvent, the mixture is reacted at 110 to 135℃for 1 to 4 hours.
In the above preparation method, preferably, in the preparation step of the magnesium halide support, the system is cooled to 50 to 70 ℃, halogenated hydrocarbon is added thereto, and the reaction is carried out for 0.5 to 1 hour.
In the above-mentioned production method, preferably, in the production step of the magnesium halide support, the inert gas may include high-purity nitrogen gas.
In the above-mentioned production method, preferably, in the production step of the magnesium halide support, the inert solvent includes one or a combination of several of alkane solvents, and a conventional inert alkane solvent such as, but not limited to, n-decane and the like may be employed. Preferably, the inert solvent may be used in an amount of 20 to 50mL/g magnesium dihalide.
In the above preparation method, the preparation step of the magnesium halide support may be performed under stirring conditions, and the rotation speed of stirring may be adjusted conventionally by those skilled in the art according to practical circumstances.
In the above preparation method, after the preparation step of the magnesium halide carrier obtains the mixed system containing the magnesium halide carrier, conventional operations such as rapid cooling of the system can be selectively performed to solidify the particles, thereby obtaining the solid magnesium halide carrier. The mixed system containing the magnesium halide carrier can be directly used for the subsequent preparation of the catalyst without a curing step. The invention preferably does not cure, but rather uses the mixed system containing the magnesium halide support directly for the subsequent preparation of the catalyst.
In the above-mentioned production method, preferably, in step S1, a mixed system containing a magnesium halide support (obtained by the above-mentioned production step of the magnesium halide support) is added dropwise to a mixed solution of a titanium compound having a Ti-halogen bond and an inert solvent, which is maintained at a temperature of 0 ℃. The dripping can be performed within 1.5-2.5 hours by adopting a peristaltic pump.
In the above-mentioned production method, preferably, in step S1, the inert solvent includes one or a combination of several of an alkane solvent and an aromatic hydrocarbon solvent, etc., such as, but not limited to, toluene, etc. More preferably, the mass ratio of the inert solvent to the magnesium halide support in step S1 is (12 to 18): 1.
in the above preparation method, preferably, the mass ratio of the titanium compound having a Ti-halogen bond to the magnesium halide support is (25 to 32): 1.
in the above-mentioned production method, preferably, in step S1, the nonionic surfactant includes one or a combination of several of polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene ethers, polymethacrylates, and the like. More preferably, the nonionic surfactant is a polymethacrylate.
In the above preparation method, preferably, in step S1, the dosage ratio of the nonionic surfactant to the magnesium halide support is (0.1 to 0.3) mL:1g.
In the above preparation method, it is preferable that in step S1, the temperature is raised to 105 to 120 ℃ for 1 to 3 hours.
In the above preparation method, preferably, in step S1, the solid-liquid separation may be performed by hot filtration or the like.
In the above-mentioned production method, preferably, in step S2, the inert solvent includes one or a combination of several of an alkane solvent and an aromatic hydrocarbon solvent, etc., such as, but not limited to, toluene, etc. More preferably, the mass ratio of the inert solvent to the first solid product in step S2 is (12 to 18): 1.
in the above-mentioned production method, preferably, in step S2, the mass ratio of the titanium compound having a Ti-halogen bond to the first solid product is (25 to 32): 1.
in the above-mentioned production method, preferably, in step S2, 0.05 to 0.6mol of the built-in internal electron donor compound is added per mol of Mg in the magnesium halide support.
In the above preparation method, preferably, in step S2, the solid-liquid separation may be performed by hot filtration or the like. After solid-liquid separation, washing and other steps may be performed to obtain the 1-butene polymerization catalyst. Preferably, the washing process may specifically be: and (3) washing the second solid product obtained after the solid-liquid separation in the step (S2) for 1-3 times by adopting toluene at 80-100 ℃, and then fully washing by adopting normal hexane at 50-70 ℃ until no precipitated titanium compound is detected in the cleaning liquid, thereby obtaining the 1-butene polymerization catalyst.
The preparation method of the 1-butene polymerization catalyst provided by the invention adopts a one-step method to prepare the spherical magnesium halide carrier type solid catalyst, and avoids the defects of low titanium carrying temperature, large titanium tetrachloride consumption and the like of the conventional polymerization catalyst. The catalyst prepared by the invention has the advantages of smooth surface, good sphericity, narrow particle size distribution, high catalytic activity, good copolymerization performance of the catalyst and the like.
The third aspect of the invention provides an application of the 1-butene polymerization catalyst in homo-polymerization or copolymerization of 1-butene.
According to a specific embodiment of the invention, preferably, the application comprises the steps of: homo-or co-polymerizing reactants comprising 1-butene in the presence of the 1-butene polymerization catalyst, an alkyl aluminum compound and an external electron donor compound to obtain a polybutene-1 homopolymer or polybutene-1 copolymer.
In the above application, preferably, the alkyl aluminum compound includes one or a combination of several of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and the like. Preferably, the alkyl aluminum compound is triethylaluminum.
In the above application, the external electron donor compound may be used as an external electron donor compound conventional in the art, and preferably, the external electron donor compound includes an alkoxysilane compound. More preferably, the external electron donor compound includes one or a combination of several of diphenyl dimethoxy silane, dicyclopentyl dimethoxy silane, propyl triethoxy silane, phenyl triethoxy silane, cyclohexyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, diisopropyl dimethoxy silane, diisobutyl dimethoxy silane, and the like. Further preferably, the external electron donor compound is cyclohexylmethyldimethoxysilane.
In the above application, preferably, the ratio of the alkyl aluminum compound to the 1-butene polymerization catalyst is (10 to 1000) in terms of aluminum to titanium molar ratio: 1, more preferably (50 to 500): 1, further preferably 300:1.
in the above application, preferably, the molar ratio of the external electron donor compound to titanium in the 1-butene polymerization catalyst is (10 to 50): 1, a step of; more preferably (15 to 20): 1.
in the above application, preferably, the 1-butene polymerization catalyst is used in an amount of: 30000 to 140000g of 1-butene per g of the 1-butene polymerization catalyst.
In the above application, preferably, the reactant comprising 1-butene comprises an alpha-olefin comonomer comprising a C2-C10 alpha-olefin; more preferably, the alpha-olefin comonomer may comprise ethylene and/or propylene.
In the above application, the reaction temperature of the homo-polymerization or copolymerization is preferably 20 to 100 ℃, the reaction pressure is 1.0 to 4.0MPa, and the reaction time is preferably 0.5 to 5 hours. More preferably, the reaction temperature of the homo-polymerization or copolymerization is 60-80 ℃, the reaction pressure is 1.5-2.5 MPa, and the reaction time is 1.5-2.5 hours.
In one embodiment of the invention, the application comprises the steps of: the reaction kettle is replaced by high-purity nitrogen for 3 times, 1-butene liquid is added, a comonomer is optionally added, hydrogen is then introduced, then the external electron donor compound, the alkyl aluminum compound and the 1-butene polymerization catalyst are pressed in by the high-purity nitrogen, the pressure is complemented to 1.0-4.0 MPa (preferably 1.5-2.5 MPa) by the nitrogen, the reaction is carried out for 0.5-5 hours (preferably 1.5-2.5 hours) at 20-100 ℃ (preferably 60-80 ℃), after the polymerization is completed, the pressure is relieved, and the product is pressed out by the nitrogen, so as to obtain the polybutene-1 homopolymer or polybutene-1 copolymer. The polymerization may be carried out in the absence or presence of a solvent, which may be a solvent conventionally used in the art, such as, but not limited to, hexane, etc., and the amount thereof may be adjusted as conventionally performed by those skilled in the art.
The catalyst for polymerizing 1-butene is suitable for catalyzing the polymerization of 1-butene, solves the problems of low isotacticity of polymers and difficult regulation and control of molecular weight distribution of polymers existing in the conventional catalyst, and can prepare the polybutene-1 resin with high isotacticity and adjustable molecular weight and molecular weight distribution, thereby improving the performance of the polybutene-1 resin, improving the processability of the resin, reducing the processing cost and widening the application field of the polybutene-1 resin.
The invention provides a 1-butene polymerization catalyst, a preparation method and application thereof. The technical scheme of the invention has at least the following beneficial effects:
1. the defects of low titanium carrying temperature and large titanium tetrachloride consumption of the conventional catalyst are avoided, and the prepared catalyst has the advantages of smooth surface, good sphericity, narrow particle size distribution and the like, and has high catalytic activity, high directionality, excellent copolymerization performance and good hydrogen regulation, and the activity of the catalyst can reach 25.4KgPB/g Cat.h;
2. the problems that the isotacticity of a polymer prepared by a conventional catalyst is low and difficult to regulate and control are solved, and the catalyst can be used for preparing the polybutene-1 resin with high isotacticity and adjustability, and the isotacticity of the polymer can be controlled to be 97.2% -99.0%;
3. Solves the problem that the molecular weight and the molecular weight distribution of the polymer are difficult to regulate and control, the catalyst can be used for preparing the polybutene-1 resin with adjustable molecular weight and molecular weight distribution, and the molecular weight of the polymer can be controlled to be 15 multiplied by 10 4 ～85×10 4 g/mol, and the molecular weight distribution can be regulated and controlled between 3.0 and 16.
Therefore, the technical scheme of the invention improves the performance of the polybutene-1 resin, improves the processability of the resin, reduces the processing cost and widens the application field of the polybutene-1 resin.
Drawings
Fig. 1 is a topographical view of the catalyst provided in example 1.
FIG. 2 is a topographical view of the catalyst provided in comparative example 2
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
In one embodiment of the invention, the 1-butene polymerization catalyst provided by the invention is prepared by the following steps:
(1) Under the protection of inert gas (such as high-purity nitrogen) and stirring, anhydrous magnesium chloride and organic alcohol are mixed in an inert solvent, and the mixture is heated to 110-135 ℃ to react for 1-4 hours to obtain a homogeneous reaction product; wherein the molar ratio of the organic alcohol to the anhydrous magnesium chloride is (2.0-4.0): 1, a step of; the organic alcohol comprises one or a combination of a plurality of organic alcohols of C2-C8, preferably the organic alcohol comprises one or a combination of a plurality of ethanol, propanol, n-butanol, isobutanol, n-hexanol, n-octanol, isooctanol and the like, more preferably the organic alcohol is isooctanol; the dosage of the inert solvent is 20-50 mL/g anhydrous magnesium chloride; the inert solvent comprises one or a combination of several alkane solvents, such as, but not limited to, n-decane and the like;
(2) Cooling the homogeneous reaction product to 50-70 ℃, adding halogenated hydrocarbon, continuously stirring for 0.5-1 hour, and cooling to room temperature to obtain a mixed system containing a magnesium halide carrier; wherein the mass ratio of the halogenated hydrocarbon to the magnesium dihalide is (2.5-4): 1, a step of; the halogenated hydrocarbon comprises one or a combination of more of 1-chloroethane, 1-chloropropane, 1-chlorobutane, 1-chlorohexane and the like, and preferably the halogenated hydrocarbon is 1-chlorobutane;
(3) Dropwise adding the mixed system containing the magnesium halide carrier into a mixed solution of titanium tetrachloride and an inert solvent, which are kept at 0 ℃ within 1.5-2.5 hours under the stirring condition, adding a nonionic surfactant after the dropwise adding, then keeping the temperature at-10-25 ℃ for 0.5-1 hour, heating to 105-120 ℃ under the stirring condition within 6 hours, and keeping the temperature for 1-3 hours, and carrying out solid-liquid separation (such as hot filtration separation) to obtain a first solid product; wherein, a peristaltic pump can be adopted for dropwise adding the mixed system containing the magnesium halide carrier; the mass ratio of the inert solvent to the magnesium halide carrier is (12-18): 1, a step of; the inert solvent comprises one or a combination of a plurality of alkane solvents, aromatic hydrocarbon solvents and the like, such as toluene and the like; the mass ratio of the titanium tetrachloride to the magnesium halide carrier is (25-32): 1, a step of; the dosage ratio of the nonionic surfactant to the magnesium halide carrier is (0.1-0.3) mL:1g; the nonionic surfactant comprises one or a combination of more of polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene ether, polymethacrylate and the like, and preferably the nonionic surfactant is polymethacrylate;
(4) Adding the first solid product into a mixed solution of titanium tetrachloride and an inert solvent, heating to 50-80 ℃ under stirring, adding a compound of a compound internal donor, continuously heating to 90-110 ℃ under stirring and keeping for 1-3 hours, and then performing solid-liquid separation (such as hot filtration separation) to obtain a second solid product; wherein the mass ratio of the inert solvent to the first solid product is (12-18): 1, a step of; the inert solvent comprises one or a combination of a plurality of alkane solvents, aromatic hydrocarbon solvents and the like, such as toluene and the like; the mass ratio of the titanium tetrachloride to the first solid product is (25-32): 1, a step of; adding 0.05-0.6 mol of the built-in internal electron donor compound per mol of Mg in the magnesium halide carrier; the compound internal electron donor compound comprises a combination of a phthalate compound, a 1, 3-diether compound and a succinate compound, wherein the mole ratio of the phthalate compound to the 1, 3-diether compound to the succinate compound is 1: (0.1-0.5): (0.2-0.8), wherein the phthalate compound comprises one or more of dibutyl phthalate (DNBP), diisobutyl phthalate (DIBP), dicyclohexyl phthalate (DCHP), diisooctyl phthalate (DIOP), dineopentyl phthalate (DPP) and the like, the 1, 3-diether compound comprises one or more of 2, 2-diisopropyl-1, 3-dimethoxypropane (DIPDMOP), 2-diisobutyl-1, 3-dimethoxypropane (DIBDMOP), 2-diphenyl-1, 3-dimethoxypropane (DPDBMOP) and the like, and the succinate compound comprises one or more of diethyl 2, 3-diisopropylsuccinate (DIPSDE), diethyl 2, 3-diisobutylsuccinate (DIBSDE), dimethyl 2, 3-diisopropylsuccinate (DIPSDM) and dimethyl 2, 3-diisobutylsuccinate (DIBSDM) and the like;
(5) And washing the second solid product with toluene at 80-100 ℃ for 1-3 times, and then washing with normal hexane at 50-70 ℃ fully until no precipitated titanium compound is detected in the cleaning liquid, thereby obtaining the 1-butene polymerization catalyst, which is a spherical magnesium chloride carrier type solid catalyst.
The compositions of the catalysts prepared in the following examples and comparative examples were measured as follows:
the Ti content in the catalyst is measured by an ultraviolet spectrophotometer (CARY-300);
the internal electron donor content in the catalyst was measured by gas chromatograph (SP 3420).
The polymerization activities of the catalysts prepared in the following examples and comparative examples were calculated according to the following formulas:
W poly ＝Q/w cat ，gPoly·g -1 cat, wherein W poly For catalyst polymerization activity, Q is the yield of polymer (g), w in 2 hours of polymerization cat The catalyst is used in an amount.
The test methods for the polymers prepared in the following examples and comparative examples are as follows:
isotacticity-the weight percentage of insoluble substances after diethyl ether extraction;
molecular weight M w -gas gel permeation chromatography (PL-220);
molecular weight distribution PD-gas gel permeation chromatography (PL-220).
Example 1
The embodiment provides a 1-butene polymerization catalyst which is prepared by the following steps:
(1) Under the protection of high-purity nitrogen, adding 90mL of n-decane, 3.0g of anhydrous magnesium chloride and 12.4mL of isooctanol into a reactor with a mechanical stirrer in sequence under the stirring condition, and heating to 130 ℃ for reacting for 2 hours to obtain a homogeneous reaction product;
(2) Cooling the homogeneous reaction product to 60 ℃, adding 10mL of 1-chlorobutane, continuously stirring for 0.5 hour, and cooling to room temperature to obtain a mixed system containing a magnesium halide carrier;
(3) The mixed system containing the magnesium halide carrier is added dropwise to 50mL TiCl with the temperature kept at 0 ℃ within 2 hours by using a peristaltic pump 4 And 50mL tolueneAdding 0.5mL of polymethacrylate into the solution after the dripping is completed, then keeping the temperature at 25 ℃ for 0.5 hour, heating to 110 ℃ within 6 hours, keeping the temperature at 110 ℃ for 2 hours, and obtaining a first solid product after hot filtration and separation;
(4) The first solid product was added to 50mL TiCl 4 And 50mL of toluene, heating to 60 ℃, adding a compound of a built-in internal electron donor, wherein the compound of the built-in internal electron donor is 4.8mmoL diisobutyl phthalate, 0.5mmoL of 2, 2-diisopropyl-1, 3-dimethoxypropane and 1.0mmoL of diethyl 2, 3-diisopropyl succinate, the molar ratio of the added compound of the built-in internal electron donor to Mg in the magnesium halide carrier is 0.2:1, the temperature is continuously raised to 100 ℃ and kept at 100 ℃ for 2 hours, and then the second solid product is obtained after hot filtration and separation;
(5) And washing the second solid product with 100mL of toluene at 90 ℃ for 2 times, and then fully washing with normal hexane at 60 ℃ until no precipitated titanium compound is detected in the cleaning liquid, thereby obtaining the 1-butene polymerization catalyst, which is a spherical magnesium chloride carrier type solid titanium catalyst.
The morphology of the catalyst is shown in figure 1 (different magnification), and the catalyst has smooth surface, good sphericity and average particle diameter of 49.2 μm.
The detection shows that the mass percentage of each component in the catalyst is Ti=2.54%, and ID (compound of the complex electron body) =6.9%.
The embodiment also provides the application of the 1-butene polymerization catalyst in the polymerization of 1-butene, wherein the application comprises the following steps:
3 times of replacement of a 5L stainless steel reaction kettle by high-purity nitrogen, adding 2.5L 1-butene liquid, introducing 0.1MPa hydrogen, then pressing 0.15mmol of cyclohexylmethyl dimethoxy silane (external electron donor compound), 3.0mmol of triethylaluminum and 0.01mmol (based on the molar amount of titanium) of the 1-butene polymerization catalyst into the reaction kettle by high-purity nitrogen, supplementing the pressure to be 2.0MPa with nitrogen, heating to 70 ℃ and reacting for 2 hours; after the polymerization was completed, the pressure was released, and the product was pressed out with nitrogen gas, and dried under vacuum at 45℃to constant weight, 480g of polybutene-1 was obtained.
The calculation and the detection show that the catalytic activity is 25.4KgPB/gCat, the isotacticity of the polymer is 98.5 percent, and the molecular weight (M w )＝62×10 4 g/mol, molecular weight distribution (PD) =7.6.
The catalyst preparation method and polymerization method of examples 2 to 6 are basically the same as example 1, except that the compound of the internal donor is different, the specific added compound and the added amount are shown in Table 1, and the polymerization result is shown in Table 2.
TABLE 1 internal Electron donor added in catalyst preparation, dosage and content of each component in catalyst
Comparative example 1
The comparative example provides a 1-butene polymerization catalyst prepared by the steps of:
(1) Under the protection of high-purity nitrogen, adding 90mL of n-decane, 3.0g of anhydrous magnesium chloride and 12.4mL of isooctanol into a reactor with a mechanical stirrer in sequence under the stirring condition, and heating to 130 ℃ for reacting for 2 hours to obtain a homogeneous reaction product;
(2) 1g of Phthalic Anhydride (PA) is added into the homogeneous reaction product, and the mixture is reacted for 2 hours at 130 ℃ and cooled to room temperature, thus obtaining a mixed system containing magnesium halide carrier;
(3) The mixed system containing the magnesium halide carrier is dripped into 100mL TiCl with the temperature kept at-10 ℃ in 2 hours by utilizing a peristaltic pump 4 After the dripping is completed, the temperature is kept at-10 ℃ for 0.5 hour, then the temperature is increased to 110 ℃ within 6 hours, the temperature is kept at 110 ℃ for 2 hours, and the first solid product is obtained after hot filtration and separation;
(4) The first solid product was added to 50mL TiCl 4 And 50mL of toluene, heating to 100deg.C, adding internal feed6.3mmol of electron compound diisobutyl phthalate (DIBP), wherein the mol ratio of the added internal electron compound to Mg in the magnesium halide carrier is 0.2:1, continuously heating to 110 ℃ and keeping at 110 ℃ for 2 hours, and then obtaining a second solid product after hot filtration and separation;
(5) The second solid product was added to 50mL TiCl 4 And 50mL of heptane, reacting for 2 hours at 98 ℃, and then separating by hot filtration to obtain a third solid product;
(6) And (3) fully washing the third solid product by adopting normal hexane at 60 ℃ until no precipitated titanium compound is detected in the cleaning liquid, thereby obtaining the 1-butene polymerization catalyst which is a magnesium chloride carrier type solid titanium catalyst.
The detection shows that the mass percentage of each component in the catalyst is Ti=1.97% and DIBP=3.79%.
The present comparative example also provides the use of the 1-butene polymerization catalyst in the polymerization of 1-butene, the use comprising the steps of:
3 times of replacement of a 5L stainless steel reaction kettle by high-purity nitrogen, adding 2.5L 1-butene liquid, introducing 0.1MPa hydrogen, pressing 0.15mmol of cyclohexylmethyl dimethoxy silane (external electron donor compound), 3.0mmol of triethylaluminum and 0.01mmol (based on the molar amount of titanium) of the 1-butene polymerization catalyst into the reaction kettle by high-purity nitrogen, supplementing the pressure to a total pressure of 2.0MPa by nitrogen, and heating to 70 ℃ for 2 hours; after the polymerization was completed, the pressure was released, and the product was pressed out with nitrogen gas, and dried under vacuum at 45℃to constant weight, to obtain 300g of polybutene-1.
The calculation and detection show that the catalytic activity is 12.1KgPB/gCat, the polymer isotacticity is 94.2%, and the molecular weight (M w )＝54×10 4 g/mol, molecular weight distribution (PD) =6.0.
Comparative example 2
The comparative example provides a 1-butene polymerization catalyst prepared by the steps of:
(1) Adding anhydrous magnesium chloride and absolute ethyl alcohol into a stirring reactor subjected to anhydrous anaerobic treatment according to the mol ratio of 1:4 and the weight ratio of the anhydrous magnesium chloride to the liquid paraffin oil of 1:4, and stirring at 100 ℃ for 2 hours to obtain a transparent magnesium chloride alkoxide solution; spraying the solution into octane at the temperature of minus 10 ℃ in a volume ratio of 5:1, standing for 2 hours at the temperature of minus 10 ℃, filtering, adding a large amount of hexane for washing for 6 times, filtering, and drying to obtain a spherical magnesium chloride carrier;
(2) 3 times of vacuumizing and argon replacement are carried out on the reactor, titanium tetrachloride is added, the spherical magnesium chloride carrier obtained in the step (1) is dropwise added into titanium tetrachloride at the temperature of minus 10 ℃, wherein the volume mass ratio of the titanium tetrachloride to the spherical magnesium chloride carrier is 20mL to 1g, stirring reaction is carried out at the temperature of minus 10 ℃ for 0.5 hour, heating is started, the temperature is slowly increased to 130 ℃ for 4 hours, 6.3mmol of an internal electron donor compound 2-isopropyl-2 isopentyl-1, 3-dimethoxypropane is added, the molar ratio of the added 2-isopropyl-2 isopentyl-1, 3-dimethoxypropane to magnesium in the carrier is 0.2:1, and the reaction is carried out at the temperature of 130 ℃ for 4 hours, and suction filtration is carried out;
(3) Adding titanium tetrachloride into the product obtained in the step (2), wherein the volume-mass ratio of the titanium tetrachloride to the spherical magnesium chloride carrier is 20 mL/1 g, heating to 130 ℃, reacting for 8 hours at constant temperature, and suction filtering;
(4) Adding a large amount of hexane into the product obtained in the step (3), washing at 60 ℃, filtering, and repeating for 6 times;
(5) Adding trihexyl aluminum/hexane solution with the volume ratio of 1:1 into the product obtained in the step (4), reacting for 0.5 hour at the constant temperature of 60 ℃ and carrying out suction filtration, wherein the molar ratio of trihexyl aluminum to magnesium in the spherical magnesium chloride carrier is 0.05:1;
(6) And (3) adding a large amount of hexane into the product obtained in the step (5), washing for 1 time at 60 ℃, carrying out suction filtration, and carrying out vacuum drying to obtain the solid catalyst.
The morphology of the catalyst is shown in figure 2, and it can be seen that the catalyst has a non-smooth surface, poor sphericity and agglomeration.
The titanium content in the catalyst was found to be 2.35 wt.%, the internal electron donor compound 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane was found to be 9.6 wt.%, and the aluminum content was found to be 1.58 wt.%.
The present comparative example also provides the use of the 1-butene polymerization catalyst in the polymerization of 1-butene, the specific procedure of which is the same as that of comparative example 1, giving 350g of polybutene-1.
The calculation and the detection show that the catalytic activity is 17.2KgPB/gCat, the polymer isotacticity is 96.8 percent, and the molecular weight (M w )＝55×10 4 g/mol, molecular weight distribution (PD) =5.8.
Comparative example 3
The comparative example provides a 1-butene polymerization catalyst, the preparation method and polymerization method of which are basically the same as those of example 1, except that the compound internal donor compound added in the comparative example is: 4.8mmoL of diisobutyl phthalate and 1.5mmoL of 2, 2-diisopropyl-1, 3-dimethoxypropane, the molar ratio of the added built-in internal electron donor compound to Mg in the magnesium halide support was 0.2:1.
The detection shows that the mass percentage of each component in the catalyst is Ti=2.61%, and ID (compound of the complex electron body) =4.8%.
320g of polybutene-1 was obtained by polymerization, which was found by calculation and detection to have a catalytic activity of 17.4 KBB/gCat, a polymer isotacticity of 96.0% and a molecular weight (M w )＝30×10 4 g/mol, molecular weight distribution (PD) =4.5.
Comparative example 4
The comparative example provides a 1-butene polymerization catalyst, the preparation method and polymerization method of which are basically the same as those of example 1, except that the compound internal donor compound added in the comparative example is: 1.5mmol of 2, 2-diisopropyl-1, 3-dimethoxypropane and 4.8mmoL of diethyl 2, 3-diisopropylsuccinate, the molar ratio of the added compound internal donor compound to Mg in the magnesium halide carrier being 0.2:1.
The detection shows that the mass percentage of each component in the catalyst is Ti=2.89%, and ID (compound of the complex electron body) =4.6%.
Polymerization gave 300g of polybutene-1, which was calculated and detected to give a catalytic activity of 18.1 KBB/gCat, a polymer isotacticity of 94.0% and a molecular weight (M w )＝28×10 4 g/mol, molecular weight distribution (PD) =8.9.
Comparative example 5
The comparative example provides a 1-butene polymerization catalyst, the preparation method and polymerization method of which are basically the same as those of example 1, except that the compound internal donor compound added in the comparative example is: 0.5mmoL of diisobutyl phthalate, 1.5mmoL of 2, 2-diisopropyl-1, 3-dimethoxypropane and 4.3mmoL of diethyl 2, 3-diisopropyl succinate are added in a molar ratio of 0.2:1 of the built-up internal electron donor compound to Mg in the magnesium halide support.
The detection shows that the mass percentage of each component in the catalyst is Ti=2.15%, and ID (compound of the complex electron body) =3.6%.
326g of polybutene-1 was obtained by polymerization, and it was found by calculation and detection that the catalytic activity was 14.6 KBB/gCat, the isotacticity of the polymer was 94.4%, the molecular weight (M w )＝25×10 4 g/mol, molecular weight distribution (PD) =8.6.
Table 2 polymerization results for the catalysts of examples and comparative examples
From the above results, it can be seen that, in example 1, compared with comparative examples 1 and 2, the titanium carrying temperature of example 1 can be raised to room temperature with the same amount of the internal electron donor compound, and the amount of titanium tetrachloride can be significantly reduced, reducing environmental pollution and injury to human. The catalyst prepared by the embodiment of the invention has the advantages of smooth surface, good sphericity, narrow particle size distribution and the like, and the catalytic activity can reach 25.4KgPB/g Cat.h. As can be seen from examples 1 to 6, the isotacticity of the polymer can be controlled to be 97.2 to 99.0 percent and the molecular weight of the polymer can be controlled to be 15X 10 by adopting the compound internal electron donor compound of the invention and adjusting the addition amount thereof 4 ～85×10 4 g/mol, and the molecular weight distribution is regulated and controlled between 3.0 and 16.
In conclusion, the spherical polybutene-1 catalyst prepared by the one-step method has the advantages of smooth surface, good sphericity, narrow particle size distribution and the like, and has the advantages of high catalytic activity, high directionality, excellent copolymerization performance, good hydrogen regulation and the like. The catalyst of the invention is used for catalyzing the polymerization of 1-butene, thus improving the performance of the polybutene-1 resin, improving the processability of the resin, reducing the processing cost and widening the application field of the polybutene-1 resin.

Claims (42)

1. A 1-butene polymerization catalyst comprising: a magnesium halide carrier, and a titanium compound with Ti-halogen bond and a compound internal electron donor compound loaded on the carrier, wherein the compound internal electron donor compound comprises a combination of phthalate compound, 1, 3-diether compound and succinate compound; wherein, based on the total weight of the 1-butene polymerization catalyst being 100%, the weight percentage of Ti is 1.8-7.0%, the weight percentage of the compound internal electron donor compound is 1.0-12.0%, and the balance is the magnesium halide carrier;
the molar ratio of the phthalate compound, the 1, 3-diether compound and the succinate compound is 1: (0.1-0.5): (0.2-0.8);
the 1-butene polymerization catalyst is prepared by the following steps:
s1, adding a magnesium halide carrier into a mixed solution of a titanium compound with Ti-halogen bond and an inert solvent, adding a nonionic surfactant, then keeping the temperature at-10 to 25 ℃ for 0.5 to 1 hour, heating to 105 to 120 ℃ and keeping the temperature for 1 to 3 hours, and carrying out solid-liquid separation to obtain a first solid product;
s2, adding the first solid product into a mixed solution of a titanium compound with Ti-halogen bond and an inert solvent, adding a compound internal electron donor compound at 50-80 ℃, heating to 90-110 ℃ and keeping for 1-3 hours, and then at least carrying out solid-liquid separation to obtain the 1-butene polymerization catalyst.
2. The 1-butene polymerization catalyst of claim 1 wherein the phthalate compound comprises one or a combination of several of dibutyl phthalate, diisobutyl phthalate, dicyclohexyl phthalate, diisooctyl phthalate and dineopentyl phthalate.
3. The catalyst for polymerizing 1-butene according to claim 1, wherein the 1, 3-diether compound comprises one or a combination of several of 2, 2-diisopropyl-1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane and 2, 2-diphenyl-1, 3-dimethoxypropane.
4. The 1-butene polymerization catalyst of claim 1 wherein the succinate compound comprises one or a combination of several of diethyl 2, 3-diisopropylsuccinate, diethyl 2, 3-diisobutylsuccinate, dimethyl 2, 3-diisopropylsuccinate and dimethyl 2, 3-diisobutylsuccinate.
5. The 1-butene polymerization catalyst according to claim 1 wherein the titanium compound having Ti-halogen bond comprises one or a combination of several of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium trichloroethoxy, titanium methoxytrichloride, titanium propoxytrichloride, titanium n-butoxytrichloride, titanium dimethoxy dichloride, titanium dichloro diethoxide, titanium dipropoxy dichloride, titanium di-n-butoxy dichloride, titanium trimethoxy chloride, titanium triethoxy chloride, titanium tripropoxy chloride and titanium tri-n-butoxy chloride.
6. The catalyst for polymerization of 1-butene according to claim 5 wherein the titanium compound having a Ti-halogen bond is titanium tetrachloride.
7. The catalyst for polymerization of 1-butene according to claim 1, wherein the magnesium halide support is prepared by the steps of: under the protection of inert gas, mixing magnesium dihalide and organic alcohol in an inert solvent, reacting for a period of time at a proper temperature, then cooling the system to the proper temperature, adding halogenated hydrocarbon into the system, and reacting for a period of time to obtain a mixed system containing a magnesium halide carrier.
8. The 1-butene polymerization catalyst of claim 7, wherein the magnesium dihalide comprises one or a combination of several of magnesium chloride, magnesium bromide and magnesium iodide.
9. The butene-1 polymerization catalyst of claim 8 wherein the magnesium dihalide is magnesium chloride.
10. The 1-butene polymerization catalyst of claim 7 wherein the organic alcohol comprises one or a combination of several of C2-C8 organic alcohols.
11. The 1-butene polymerization catalyst of claim 10, wherein the organic alcohol comprises one or a combination of ethanol, propanol, n-butanol, isobutanol, n-hexanol, n-octanol, and isooctanol.
12. The butene-1 polymerization catalyst of claim 11 wherein the organic alcohol is isooctanol.
13. The 1-butene polymerization catalyst of claim 7 wherein the molar ratio of the organic alcohol to the magnesium dihalide is (2.0-4.0): 1.
14. the 1-butene polymerization catalyst of claim 7 wherein the halogenated hydrocarbon comprises one or a combination of several of 1-chloroethane, 1-chloropropane, 1-chlorobutane and 1-chlorohexane.
15. The 1-butene polymerization catalyst of claim 14 wherein the halogenated hydrocarbon is 1-chlorobutane.
16. The catalyst for polymerization of 1-butene according to claim 7 wherein the mass ratio of the halogenated hydrocarbon to the magnesium dihalide is (2.5 to 4): 1.
17. the catalyst for polymerization of 1-butene according to claim 7 wherein the magnesium dihalide and the organic alcohol are reacted at 110 to 135 ℃ for 1 to 4 hours after being mixed in an inert solvent.
18. The catalyst for polymerization of 1-butene according to claim 7 wherein the system is cooled to 50 to 70 ℃, halogenated hydrocarbon is added thereto and reacted for 0.5 to 1 hour.
19. The butene-1 polymerization catalyst of claim 7 wherein the inert solvent comprises one or a combination of alkane solvents.
20. The catalyst for polymerization of 1-butene according to claim 7 wherein the inert solvent is used in an amount ranging from 20 to 50mL/g of magnesium dihalide.
21. A process for preparing the catalyst for polymerization of 1-butene according to any of claims 1 to 20 comprising the steps of:
s1, adding a magnesium halide carrier into a mixed solution of a titanium compound with Ti-halogen bond and an inert solvent, adding a nonionic surfactant, then keeping the temperature at-10 to 25 ℃ for 0.5 to 1 hour, heating to 105 to 120 ℃ and keeping the temperature for 1 to 3 hours, and carrying out solid-liquid separation to obtain a first solid product;
s2, adding the first solid product into a mixed solution of a titanium compound with Ti-halogen bond and an inert solvent, adding a compound internal electron donor compound at 50-80 ℃, heating to 90-110 ℃ and keeping for 1-3 hours, and then at least carrying out solid-liquid separation to obtain the 1-butene polymerization catalyst.
22. The production method according to claim 21, wherein in step S1, the mixed system containing the magnesium halide support is added dropwise to a mixed solution of a titanium compound having a Ti-halogen bond and an inert solvent maintained at a temperature of 0 ℃.
23. The production method according to claim 21, wherein in step S1, the inert solvent comprises one or a combination of several of an alkane solvent and an aromatic hydrocarbon solvent.
24. The production method according to claim 21, wherein the mass ratio of the inert solvent to the magnesium halide support in step S1 is (12 to 18): 1.
25. the production method according to claim 21, wherein in step S1, the mass ratio of the titanium compound having a Ti-halogen bond to the magnesium halide support is (25 to 32): 1.
26. the preparation method of claim 21, wherein in step S1, the nonionic surfactant comprises one or a combination of several of polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene ethers, and polymethacrylates.
27. The method of claim 26, wherein the nonionic surfactant is a polymethacrylate.
28. The production method according to claim 21, wherein in step S1, the ratio of the nonionic surfactant to the magnesium halide support is (0.1 to 0.3) mL:1g.
29. The production method according to claim 21, wherein in step S2, the inert solvent comprises one or a combination of several of an alkane solvent and an aromatic hydrocarbon solvent.
30. The production method according to claim 21, wherein a mass ratio of the inert solvent to the first solid product in step S2 is (12 to 18): 1.
31. The production method according to claim 21, wherein in step S2, the mass ratio of the titanium compound having a Ti-halogen bond to the first solid product is (25 to 32): 1.
32. the production method according to claim 21, wherein in step S2, 0.05 to 0.6mol of the built-in internal electron donor compound is added per mol of Mg in the magnesium halide support.
33. Use of the 1-butene polymerization catalyst of any of claims 1-20 in homo-or co-polymerization of 1-butene.
34. The application of claim 33, wherein the application comprises the steps of: homo-or co-polymerizing reactants comprising 1-butene in the presence of the 1-butene polymerization catalyst, an alkyl aluminum compound and an external electron donor compound to obtain a polybutene-1 homopolymer or polybutene-1 copolymer.
35. The use of claim 34, wherein the alkyl aluminum compound comprises one or a combination of several of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum.
36. The use of claim 34, wherein the external electron donor compound comprises an alkoxysilane compound.
37. The use of claim 36, wherein the external electron donor compound comprises one or a combination of diphenyl dimethoxy silane, dicyclopentyl dimethoxy silane, propyl triethoxy silane, phenyl triethoxy silane, cyclohexyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, diisopropyl dimethoxy silane, and diisobutyl dimethoxy silane.
38. Use according to claim 34, wherein the ratio of the alkyl aluminium compound to the 1-butene polymerization catalyst is in terms of aluminium to titanium molar ratio (10-1000): 1.
39. use according to claim 38, wherein the ratio of the alkyl aluminium compound to the 1-butene polymerization catalyst is (50-500) in terms of aluminium to titanium molar ratio: 1.
40. use according to claim 34, wherein the molar ratio of the external electron donor compound to titanium in the butene-1 polymerization catalyst is comprised between (10 and 50): 1.
41. the use according to claim 34, wherein the homo-or co-polymerization is carried out at a reaction temperature of 20 to 100 ℃, a reaction pressure of 1.0 to 4.0MPa and a reaction time of 0.5 to 5 hours.
42. The process according to claim 41, wherein the homo-or copolymerization is carried out at a temperature of 60 to 80℃and a pressure of 1.5 to 2.5MPa for a time of 1.5 to 2.5 hours.
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