CN111087509A - Flexible 1-butene polymer and preparation method thereof - Google Patents
Flexible 1-butene polymer and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Abstract
The invention relates to the field of olefin polymerization, and discloses a flexible 1-butene polymer and a preparation method thereof, wherein the preparation method of the flexible 1-butene polymer is carried out in a liquid phase reactor and a gas phase reactor which are connected in series, and comprises the steps of (1) carrying out slurry polymerization reaction on 1-butene and optional α -olefin in the liquid phase reactor by using liquid propane as a solvent in the presence of a Ziegler-Natta catalytic system, (2) introducing a slurry polymerization reaction product obtained in the step (1) into the gas phase reactor, and introducing 1-butene and optional α -olefin into the gas phase reactor to carry out gas phase polymerization reaction, wherein α -olefin used in the step (1) and the step (2) is respectively and independently mono-olefin with 2-10 carbon atoms at the end of a molecular chain except for 1-butene, and the 1-butene polymer prepared by the method provided by the invention has lower tensile modulus, namely better flexibility.
Description
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to a flexible 1-butene polymer and a preparation method thereof.
Background
The current poly-1-butene products mainly include both homopolymers and random copolymers. Among them, high isotactic poly-1-butene (isotactic index higher than 96%) is excellent in creep resistance, environmental stress cracking resistance and impact resistance, superior to polyethylene, and enjoys the reputation of "plastic gold", and thus is very suitable for use as pipes, such as water supply pipes, hot water pipes, industrial pipes, and building pipes. The poly-1-butylene random copolymer (comonomer is mainly ethylene) can obviously improve the softness, sealing strength and the like of the polymer, is suitable for producing film products, and is widely applied to the fields of food, sanitary product packaging and the like.
The 1-butenyl polymer is prepared mainly by a gas phase method, a solution method and a bulk method.
The gas phase method generally adopts a fluidized bed gas phase reactor, CN102040693, CN1140545C, US4503203, US3168484, US3580898, US5241024 and US3922322 all need to adopt Ziegler-Natta catalyst, 1-butene monomer directly reacts in a gas fluidized bed, and 1-butene polymer with good particle shape and controllable melt mass flow rate in a certain range and high isotactic index is synthesized and prepared. However, the gas phase method has low monomer concentration and low 1-butene monomer partial pressure, which causes low polymerization activity, generally lower than 5.0 KgPB/g-Cat, and has high ash content in the polymer, so that no industrial report is available at present.
The 1-butene polymer synthesis preparation process mostly adopts a liquid phase bulk method, wherein CN101044172, CN101056901, CN101511931, CN101528841, EP1219645, CN101687951, CN102216347 and the like all relate to the adoption of the bulk methodWhen the 1-butenyl copolymer is synthesized by a bulk method, under the high temperature condition, the 1-butene polymer is dissolved in the 1-butene, so that the viscosity of a polymerization system is large, the general viscosity is 1000-100000cP, and after the monomers are removed, the viscosity of the polymer can reach 20 x 10 at most6cP has high requirements on subsequent processing techniques and devices, and a polymer with a regular particle form cannot be directly obtained by a bulk preparation process. In order to prepare 1-butenyl polymer with good particle morphology, CN103288993 adopts a stepwise temperature raising mode to prepare 1-butenyl polymer with spherical morphology, and the bulk density of the 1-butenyl polymer is 0.30g/cm3About, the isotactic index is more than 95%, but the first stage reaction temperature is lower than 0-20 ℃, which is not beneficial to the control production of an industrial device; CN106893020 discloses a process for preparing 1-butene polymer using an alkoxysilane and ether composite external electron donor system, which comprises prepolymerizing propylene at a low temperature to form a polymer with a relatively perfect particle morphology, and then carrying out multistage 1-butene polymerization under the same polymerization conditions, thereby obtaining a 1-butene polymer with a relatively good particle morphology, but the process has a long reaction period, a low polymerization conversion rate, a high product ash content, and is not conducive to production. CN105482009B relates to a method for producing 1-butene polymer by a continuous method, which adopts a 1-butene low-temperature slurry prepolymerization reactor and a gas phase horizontal kettle reactor to be connected in series to realize the preparation of 1-butene polymer powder, uses 1-butene as a solvent in the low-temperature slurry polymerization reaction process, has long whole reaction period, does not specifically disclose the reaction in the gas phase reactor and the used monomer, and does not relate to the preparation of flexible materials.
US5237013 and CN103304709 relate to the solution polymerization of 1-butene using inert solvent n-hexane as diluent, and the generated poly-1-butene is precipitated or dissolved in solvent, which has the advantages of simple operation, easy derivation of polymerization heat from the system, convenient reaction control, etc., but the 1-butene polymer will swell or dissolve in n-hexane solvent at higher temperature, making the polymer morphology uncontrollable.
Disclosure of Invention
The present invention aims to provide a 1-butene polymer having excellent flexibility and a method for preparing the same.
Specifically, the invention provides a flexible 1-butene polymer, wherein the flexible 1-butene polymer comprises 60-99.9 wt% of a polymer component A and 0.1-40 wt% of a polymer component B, the polymer component A and the polymer component B are 1-butene polymers, and the intrinsic viscosity IV of the polymer component A is1And the intrinsic viscosity IV of the polymer component B2Each independently of the other, is 0.1 to 5dl/g, and the intrinsic viscosity ratio IV of the polymer component A to the polymer component B1/IV2Is 0.5-1.5.
The present invention also provides a process for the preparation of a flexible butene-1 polymer in a liquid phase reactor and a gas phase reactor connected in series, comprising:
(1) slurry polymerization of 1-butene and optionally α -olefin in a liquid phase reactor in the presence of a Ziegler-Natta catalyst system with liquid propane as solvent;
(2) introducing the slurry polymerization product obtained in step (1) into a gas phase reactor, and introducing 1-butene and optionally α -olefin into the gas phase reactor to carry out gas phase polymerization;
the α -olefin used in step (1) and step (2) is each independently a monoolefin having a double bond of 2 to 10 carbon atoms at the end of the molecular chain other than 1-butene.
In addition, the invention also provides the flexible 1-butene polymer prepared by the method.
The invention adopts the operation of connecting the liquid phase reactor and the gas phase reactor in series, which not only can increase the production capacity of the polymerization device and improve the utilization rate of the catalyst, but also is beneficial to regulating and optimizing the composition and the structure of the flexible 1-butene polymer product in a larger range. The preparation method of the flexible 1-butene polymer has good polymerization activity under the high-temperature polymerization condition, firstly slurry polymerization is carried out by taking liquid propane as a solvent to synthesize the granular 1-butene polymer, and then the gas-phase polymerization reaction is combined to improve the polymer rubber phase to prepare the soft 1-butene polymer, so that the problems of stickiness of a high-temperature polymerization system and difficulty in material conveying can be effectively solved, the process flow is greatly optimized, and the device equipment is simplified. In addition, the preparation method of the flexible 1-butene polymer provided by the invention has the advantages of simple process, flexible and convenient operation, low cost, low technical and equipment requirements, convenience for starting and stopping equipment for treatment, easiness for realizing industrial production, high polymerization efficiency, high polymerization activity, low VOC content, regular particle form and the like.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below.
The flexible 1-butene polymer provided by the invention contains 60-99.9 wt% of polymer component A and 0.1-40 wt% of polymer component B, wherein the polymer component A and the polymer component B are 1-butene polymers, and the intrinsic viscosity IV of the polymer component A1And the intrinsic viscosity IV of the polymer component B2Each independently of the other, is 0.1 to 5dl/g, and the intrinsic viscosity ratio IV of the polymer component A to the polymer component B1/IV2Is 0.5 to 1.5, preferably 0.8 to 1.2. Controlling the intrinsic viscosities of the polymer component a and the polymer component B within the above ranges ensures that the polymer can provide a satisfactory good balance of characteristics.
The polymer component A and the polymer component B can be 1-butene homopolymer and can also be a copolymer of 1-butene and α -olefin, wherein, the α -olefin is mono-olefin with double bond of 2-10 carbon atoms at the molecular chain end except 1-butene, preferably ethylene and/or propylene, most preferably ethylene, the polymer component A preferably comprises 92-99.9mol percent of 1-butene derived units and 0.1-8mol percent of α -olefin derived units, the polymer component B is taken as a rubber phase to ensure that the 1-butene polymer has excellent flexibility, and preferably, the polymer component B comprises 55-75mol percent of 1-butene derived units and 25-45mol percent of α -olefin derived units.
According to the invention, preferably, the bulk density of the butene-1 polymer is not less than 0.35g/cm3At 190 ℃ and 2.1The melt index under the condition of 6kg is 0.1-50g/10min, and the molecular weight distribution index is 1-10.
The flexible 1-butene polymer can be extruded and pelletized by adopting the existing extrusion and pelletizing equipment, and additives commonly used in the technical field, such as at least one of an antioxidant, a light stabilizer, a heat stabilizer, a coloring agent, a filler and the like, are added during pelletizing.
The preparation method of the flexible 1-butene polymer provided by the invention is carried out in a liquid phase reactor and a gas phase reactor which are connected in series, and comprises the following steps:
(1) slurry polymerization of 1-butene and optionally α -olefin in a liquid phase reactor in the presence of a Ziegler-Natta catalyst system with liquid propane as solvent;
(2) introducing the slurry polymerization product obtained in step (1) into a gas phase reactor, and introducing 1-butene and optionally α -olefin into the gas phase reactor to carry out gas phase polymerization.
In the present invention, the α -olefins used in step (1) and step (2) are each independently a monoolefin having a double bond of 2 to 10 carbon atoms at the terminal of the molecular chain other than 1-butene, preferably each independently ethylene and/or propylene, more preferably both ethylene.
The polymer obtained by polymerizing 1-butene and optional α -olefin in slurry polymerization is polymer A, the polymer obtained by polymerizing 1-butene and optional α -olefin in gas phase polymerization is polymer B, the boiling point difference between 1-butene and liquid propane is large, the separation of industrial production process is convenient, and the removal of volatile components such as oligomer in polymerization production is very beneficial in the propane removal process, so that the VOC content in the 1-butene polymer is reduced.
According to the present invention, although it is sufficient to ensure that the slurry polymerization uses liquid propane as a solvent, in order to obtain a butene-1 polymer having a lower VOC content and a better particle morphology, it is preferred that the liquid propane is used in an amount of 1 to 10mol, more preferably 2 to 9mol, and most preferably 3 to 6mol, relative to 1mol of butene-1.
According to the present invention, preferably, the slurry polymerization conditions comprise a temperature of 20 to 100 ℃, preferably 30 to 80 ℃, a pressure of 1 to 5MPa, preferably 2 to 4MPa, and a time of 0.1 to 5h, preferably 0.5 to 3 h; the gas phase polymerization conditions include a temperature of 55-100 deg.C, preferably 60-85 deg.C, a pressure of 0.1-2.5MPa, preferably 0.5-2.0MPa, and a time of 0.1-3h, preferably 0.1-2 h. In the present invention, the pressures are gauge pressures.
According to the invention, the step (1) and the step (2) may be added with α -olefin (copolymerization of 1-butene with α -olefin) or without (homopolymerization of 1-butene), preferably, the amount of 1-butene used in the step (1) is 92 to 99.9 mol% and α -olefin used in the step (1) is 0.1 to 8 mol%, and the amount of 1-butene used in the step (2) is 55 to 75 mol% and α -olefin used in the step (2) is 25 to 45 mol%.
The slurry polymerization is carried out in a liquid phase reactor, wherein the liquid phase reactor can be a loop reactor or a vertical stirred tank reactor, and is preferably a loop reactor.
The gas-phase polymerization reaction is carried out in a gas-phase medium, and the adopted gas-phase reactor can be a gas-phase fluidized bed reactor, a gas-phase moving bed reactor or a gas-phase stirred bed reactor, and is preferably a gas-phase fluidized bed reactor.
The Ziegler-Natta catalyst system is a stereospecific catalyst which preferably comprises a component A, a component B and a component C, wherein the component A is a magnesium chloride supported Ziegler-Natta catalyst which contains Ti and contains an internal electron donor, the component B is organic aluminum, and the component C is an external electron donor. Wherein the molar ratio of the component A to the component B is preferably 1 (10-500), more preferably 1 (25-100) in terms of titanium/aluminum. The molar ratio of component C to component B is preferably (0.005-0.5):1, more preferably (0.01-0.4): 1.
The Ziegler-Natta solid catalyst active component of component a is well known to those skilled in the art and can be prepared by methods well known in the art, for example, as disclosed in the following patent documents: CN85100997A, CN98126383.6, CN98111780.5, CN98126385.2, CN93102795.0, CN00109216.2, CN99125566.6, CN99125567.4, CN02100900.7, CN102453162, CN103819586, CN104610474, CN104610475, CN104610476, CN104610477, CN104610478, CN105622800, CN106543314, CN106543313, CN106543312, CN 10654540, CN106554439, CN107522800 and CN 107522803.
The internal electron donor in the component A can be at least one selected from carboxylic ester compounds, ether compounds, 1, 3-alcohol ester compounds and sulfonamide compounds, preferably at least one selected from phthalic ester compounds, 1, 3-diether compounds, glycol ester compounds and succinate ester compounds, and most preferably 1, 3-diether compounds.
The organoaluminum is preferably AlRnX(3-n)An alkylaluminum compound of the structure and/or an alkylaluminoxane, R is C1-C20Alkyl radical, C7-C20Aralkyl or C6-C20Aryl, X is halogen, and n is an integer of 0 to 3. Wherein the compound has AlRnX(3-n)The alkylaluminum compound of structure (la) is preferably at least one selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-butylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, dimethylaluminum monochloride, diisobutylaluminum monochloride, isobutylaluminum dichloride, tris (2-methyl-3-phenyl-butyl) aluminum and tris (2-phenyl-butyl) aluminum. The alkylaluminoxane is preferably at least one selected from the group consisting of methylaluminoxane, tetra (isobutyl) aluminoxane, tetra (2,4, 4-trimethyl-pentyl) aluminoxane, tetra (2, 3-dimethylbutyl) aluminoxane and tetra (2,3, 3-trimethylbutyl) aluminoxane.
The external electron donor may be at least one selected from the group consisting of a siloxane compound, an aminosilane compound, an organic amine compound, and an ether compound. Among them, the siloxane-based compound is preferably at least one selected from the group consisting of trimethylmethoxysilane, trimethylethoxysilane, methyl-t-butyldimethoxysilane, cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, dicyclopentyldimethoxysilane, isobutylcyclohexyldimethoxysilane, tetraethoxysilane and n-propenotriethoxysilane. The aminosilane compound is preferably at least one selected from the group consisting of diethylaminotriethoxysilane, 3-aminopropyltriethoxysilane, diethylaminomethyltriethoxysilane, dimethylaminomethyltriethoxysilane, diisopropylaminomethyltriethoxysilane, di-n-propylaminomethyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, piperidinyltriethoxysilane and pyrrolyltriethoxysilane. The organic amine compound is preferably selected from the group consisting of aziridine, azetidine, pyrrolidine, azepane, azocane, 2, 3-dimethyl aziridine, 2,3, 3-tetramethyl aziridine, 2,4, 4-tetramethyl azetidine, 2,4, 4-tetraethylazetidine, 2,3, 3-tetramethyl azetidine, 2,3, 3-tetraethylazetidine, 2,4, 4-tetramethyl pyrrolidine, 2,5, 5-tetraethylpyrrolidine, 2,5, 5-tetra-n-propyl pyrrolidine, 2,5, 5-tetraisopropyl pyrrolidine, 2,5, 5-tetraisobutylpyrrolidine, 2,6, 6-tetramethylpiperidine, 2,6, 6-tetraethylpiperidine, 2,6, 6-tetra-n-propylpiperidine, 2,6, 6-tetraisopropylpiperidine, 2,6, 6-tetraisobutylpiperidine, 2,4, 4-tetramethylpiperidine, 2,4, 4-tetraethylpiperidine, 2,5, 5-tetramethylpiperidine, 2,5, 5-tetraethylpiperidine, 2-methyl-2-cyclohexyl-6-methyl-6-ethylpiperidine, 2-dicyclopentyl-6, 6-dimethylpiperidine, 2,7, 7-tetramethylazepane, 2,7, 7-tetraethylazepane, 2,2,7, 7-tetra-n-propylazepane, 2,7, 7-tetraisopropyl azepane, 2,7, 7-tetraisobutyl azepane, 2,5, 5-tetramethylazepane, 2,5, 5-tetraethylazepane, 3,5, 5-tetramethylazepane, 3,5, 5-tetraethylazepane, 2-methyl-2-cyclohexyl-7-methyl-7-azepane, 2-dicyclopentyl-7, 7-dimethylazepane, 2,8, 8-tetramethylazocane, 2,8, 8-tetraethylazocane, 2,8, 8-tetra-n-propylazocane, 2,2,8, 8-tetraisopropyl azocane, 2,8, 8-tetra-n-butyl azocane, 2,8, 8-tetraisobutyl azocane, 2,7, 7-tetramethyl azocane, 2,6, 6-tetramethyl azocane, 3,5, 5-tetramethyl azocane and 3,3,6, 6-tetramethyl azocane. The ether compound is preferably at least one selected from the group consisting of compounds of the following general formula:
wherein R is1And R2Each independently selected from C1-C20One of linear, branched or cyclic aliphatic radicals, R3、R4、R5、R6、R7And R8Each independently selected from a hydrogen atom, a halogen atom, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl and C7-C20One of aralkyl, and R3、R4、R5、R6、R7And R8Optionally linked to form a ring. Specific examples of the ether compound include, but are not limited to: 2, 2-diisobutyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2-benzyl-1, 3-dimethoxypropane, 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isopropyl-2-3, 7-dimethyloctyl-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1, 3-dimethoxypropane, 2-diisobutyl-1, 3-diethoxypropane, 2, 2-diisobutyl-1, 3-dipropoxypropane, 2-isopropyl-2-isoamyl-1, 3-diethoxypropane, 2-isopropyl-2-isoamyl-1, 3-dipropoxypropane and at least one of 2, 2-bis (cyclohexylmethyl) -1, 3-diethoxypropane.
According to the invention, in the slurry polymerization reaction and the gas phase polymerization reaction, a chain transfer agent is generally adopted to regulate the molecular weight of the polymer, namely hydrogen with different proportions is added into a reaction system as a molecular weight regulator; the molecular weight can also be controlled by controlling the reaction temperature. When hydrogen is used as the molecular weight regulator, the partial pressure of hydrogen may be from 0.1 to 1 MPa.
In addition, a well-known prepolymerization step may be added before the slurry polymerization. The prepolymerization is to add the catalyst into a small amount of monomer for reaction at low temperature, so as to ensure that the catalyst can keep good activity and form in the subsequent polymerization. The prepolymerization can be carried out continuously in bulk or batchwise in the presence of an inert solvent, and the prepolymerization temperature can be from 5 to 30 ℃. A precontacting step may optionally be provided before the prepolymerization step. The pre-contact refers to a pre-complexing process of a solid active component of the catalyst in the presence of organic aluminum and an external electron donor to convert the solid active component of the catalyst into a catalyst system with polymerization activity, wherein the pre-contact temperature is generally 5-30 ℃.
In addition, the invention also provides the 1-butene polymer prepared by the method.
The present invention is further illustrated by the following examples. It is to be understood, however, that these examples are for the purpose of illustration and explanation only and are not intended to limit the present invention.
In the following examples and comparative examples, MgCl2/TiCl4The supported Ziegler-Natta catalyst is prepared by the following method: 200mL of white oil, 8.0g (0.08mol) of magnesium chloride, 3g (0.01mol) of octadecanol, 95mL (1.6mol) of ethanol and 9.8mL (0.08mol) of 2, 2-dimethoxypropane are added into a 1.6L reaction kettle, and the temperature is raised to 90 ℃ under stirring; after reacting at constant temperature for 1 hour, dispersing the mixture for 30 minutes by stirring at low speed (stirring speed is 400 rpm) to emulsify; adding 35mL (0.45mol) of epoxy chloropropane into the emulsified product, reacting for half an hour, and performing filter pressing for 9 minutes; washing the filter-pressing product with hexane for 5 times, and filter-pressing after washing each time, wherein the total time of the filter-pressing process is 20 minutes. Finally, vacuum drying the product to obtain a magnesium-containing carrier Z1; in a 300mL glass reaction flask, 100mL of titanium tetrachloride was added and cooled to-20 ℃,8 g of the above magnesium-containing carrier Z1 was added thereto and stirred at-20 ℃ for 30min, after which, the temperature was slowly raised to 110 ℃ and 1.5mL of diisobutyl phthalate was added during the temperature raising, the liquid was filtered after maintaining at 110 ℃ for 30min, and then titanium tetrachloride was added and washed 2 times to obtain a solid product, to which 100mL of titanium tetrachloride was added and at 25 ℃ was addedReacting for 16 hours, finally washing with hexane for 4 times, and drying to obtain MgCl2/TiCl4A supported Ziegler-Natta catalyst.
In the following examples and comparative examples, the polymer-related data were obtained according to the following test methods:
(1) melt mass flow rate (melt index, MFR): measured according to standard ISO 1133, the experimental conditions: 2.16kg, 190 ℃.
(2) Molecular weight distribution Mw/Mn: the weight average molecular weight (M) of the sample was calculated from the flow-out time by using a Waters GPC 2000 at a sample mass concentration of 0.1mg/mL, a measurement temperature of 150 ℃ and a measurement flow rate of 1mL/min, and preparing a calibration curve with the molecular weight of polystyrene as an internal referencew) Number average molecular weight (M)n) And molecular weight distribution (M)w/Mn)。
(3) Comonomer content: determined by FT-IR spectroscopy.
(4)13C-NMR measurement: performed in a deuterated o-dichlorobenzene solution of polymer (8-12 wt%) at 120 ℃ by using a 90 ° pulse, a 15s delay between pulse and CPD to remove1H-13C coupling, spectra were obtained on a Bruker AV-600 spectrometer operating at 150MHz according to the Fourier transform mode at 120 ℃ and nuclear magnetic calculations were performed with reference to Carbon-13 NMRspectral analysis of stationary polymeric derivatives from the chemical shift calculation and the polymerization mechanism.
(5) Bulk density: measured according to GB/T1636-.
(6) Rubber phase content: measured according to ASTM D5492.
(7) Tensile property: measured according to ISO 527/2-93.
(8) Intrinsic viscosity IV: measured according to GB/T1632.
(9) VOC measurement: the polymer powder was weighed using the German automobile industry Association VDA277 test standard.
Example 1
Procatalyst DQC (MgCl)2/TiCl4Supported Ziegler-Natta catalyst), cocatalyst (triethylaluminium) and external electron donor(Dicyclopentyldimethoxysilane) was precontacted at 6 ℃ for 8min and then continuously introduced into the reactor, with a Triethylaluminum (TEA) flow of 6.33g/hr, a Dicyclopentyldimethoxysilane (DCPMS) flow of 0.3g/hr, a procatalyst flow of 0.6g/hr, and a TEA/DCPMS ratio of 50 (mol/mol). The prepolymerization is carried out for 4min at 15 ℃, and the prepolymerization rate of the catalyst is about 80-120 times under the condition.
And continuously introducing the prepolymerized catalyst and the monomer into a loop reactor filled with liquid propane to complete slurry polymerization, wherein the loop polymerization temperature is 70 ℃, the reaction pressure is 2.5MPa, and the residence time is 55 min. 1-butene, a small amount of ethylene, hydrogen and liquid propane are fed into the loop reactor, wherein the feeding ratio of ethylene/1-butene is 0.01(mol/mol), the feeding ratio of hydrogen/1-butene is 350ppm (mol), and the molar using ratio of 1-butene to propane is 1: 4. Removing part of propane from the obtained polymer by flash evaporation, then feeding the polymer into a gas phase reactor, introducing 1-butene, ethylene and hydrogen into the gas phase reactor for gas phase reaction, and continuing copolymerization reaction, wherein C2/(C2+C4) 0.15(mol/mol), H2/(C2+C4) It was 0.03 (mol/mol). The reaction temperature of the gas phase reactor was 65 ℃, the reaction pressure was 0.8MPa, and the residence time was 40 min. The polymer coming out of the gas phase reactor was subjected to flash separation to obtain a flexible butene-1 copolymer, the analytical results of which are shown in Table 1.
Example 2
Example 2 the catalyst, prepolymerization, slurry polymerization and gas phase polymerization used were the same as in example 1. The difference from the embodiment 1 is that: in gas phase reactor C2/(C2+C4) Is 0.2(mol/mol) and H2/(C2+C4) 0.04(mol/mol), a residence time of 25min and the analytical results of the obtained flexible 1-butene polymer are shown in Table 1.
Example 3
The catalyst used in example 3 and the prepolymerization were the same as in example 1. The difference from the embodiment 1 is that: the feed ratio of ethylene/1-butene in the loop reactor was 0.016(mol/mol) and the feed ratio of hydrogen/1-butene was 150ppm (mol), C in the gas phase reactor2/(C2+C4) Is 0.15(mol/mol) andH2/(C2+C4) 0.02(mol/mol), a residence time of 55min and the analytical results of the obtained flexible 1-butene polymer are shown in Table 1.
Comparative example 1
The catalyst, prepolymerization, polymerization process conditions and formulation of the auxiliary and the addition of the catalyst used in comparative example 1 were the same as in example 1. Except that the second gas-phase polymerization was not conducted, the analysis results of the obtained flexible 1-butene polymer are shown in Table 1.
TABLE 1
| Item | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| C in Polymer component A2(mol％) | 2.1 | 2.2 | 3.5 | 2.1 |
| Polymer component B content (wt%) | 18.0 | 14.1 | 26.5 | - |
| C in Polymer component B2(mol％) | 26 | 35 | 27 | - |
| Polymer AIV1(dl/g) | 3.2 | 3.4 | 2.0 | 3.3 |
| Polymer B IV2(dl/g) | 3.6 | 3.3 | 1.9 | - |
| MFR(g/10min) | 1.5 | 1.6 | 8.3 | 1.6 |
| Molecular weight distribution Mw/Mn | 5.6 | 5.8 | 5.2 | 5.5 |
| Bulk Density (g/cm)3) | 0.36 | 0.38 | 0.40 | 0.39 |
| Tensile modulus (MPa) | 8.6 | 15.1 | 3.5 | 82 |
| VOC(μg·C/g) | 29 | 31 | 28 | 26 |
As can be seen from the results in Table 1, the 1-butene polymer prepared by the method provided by the present invention has a lower tensile modulus, i.e., better flexibility.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A flexible butene-1 polymer comprising 60 to 99.9% by weight of a polymer component A and 0.1 to 40% by weight of a polymer component B, wherein both the polymer component A and the polymer component B are butene-1 polymers and the polymer component A has an intrinsic viscosity IV1And the intrinsic viscosity IV of the polymer component B2Each independently of the other, is 0.1 to 5dl/g, and the intrinsic viscosity ratio IV of the polymer component A to the polymer component B1/IV2Is 0.5-1.5.
2. The 1-butene polymer according to claim 1 wherein polymer component A comprises 92 to 99.9 mol% of 1-butene derived units and 0.1 to 8 mol% of α -olefin derived units and polymer component B comprises 55 to 75 mol% of 1-butene derived units and 25 to 45 mol% of α -olefin derived units, and the α -olefin is a monoolefin having a double bond of 2 to 10 carbon atoms at the molecular chain end other than 1-butene, preferably each independently ethylene and/or propylene, more preferably all ethylene.
3. The 1-butene polymer according to claim 1 or 2 wherein the bulk density of the 1-butene polymer is not less than 0.35g/cm3The melt index at 190 deg.C under 2.16kg is 0.1-50g/10min, and the molecular weight distribution is 1-10.
4. A process for the preparation of flexible butene-1 polymers carried out in liquid and gas phase reactors connected in series, comprising:
(1) slurry polymerization of 1-butene and optionally α -olefin in a liquid phase reactor in the presence of a Ziegler-Natta catalyst system with liquid propane as solvent;
(2) introducing the slurry polymerization product obtained in step (1) into a gas phase reactor, and introducing 1-butene and optionally α -olefin into the gas phase reactor to carry out gas phase polymerization;
the α -olefins used in step (1) and step (2) are each independently a monoolefin having a double bond of 2 to 10 carbon atoms at the end of the molecular chain other than 1-butene, preferably each independently ethylene and/or propylene, more preferably both ethylene.
5. The production method according to claim 4, wherein the liquid propane is used in an amount of 1 to 10mol relative to 1mol of 1-butene during the slurry polymerization.
6. The production method according to claim 4, wherein the conditions of the slurry polymerization reaction include a temperature of 20 to 100 ℃, preferably 30 to 80 ℃, a pressure of 1 to 5MPa, preferably 2 to 4MPa, and a time of 0.1 to 5 hours, preferably 0.5 to 3 hours; the gas phase polymerization conditions include a temperature of 55-100 deg.C, preferably 60-85 deg.C, a pressure of 0.1-2.5MPa, preferably 0.5-2.0MPa, and a time of 0.1-3h, preferably 0.1-2 h.
7. The process according to claim 4, wherein the amount of butene-1 used in step (1) is 92 to 99.9 mol% and the amount of α -olefin used is 0.1 to 8 mol%, and the amount of butene-1 used in step (2) is 55 to 75 mol% and the amount of α -olefin used is 25 to 45 mol%.
8. The preparation method according to any one of claims 4 to 7, wherein the Ziegler-Natta catalyst system comprises a component A, a component B and a component C, wherein the component A is a magnesium chloride supported Ziegler-Natta catalyst containing Ti and an internal electron donor, the component B is organic aluminum, and the component C is an external electron donor;
preferably, the molar ratio of the component A to the component B is 1 (10-500), more preferably 1 (25-100), in terms of titanium/aluminum; the molar ratio of component C to component B is (0.005-0.5):1, more preferably (0.01-0.4): 1.
9. The production method according to claim 8,
the internal electron donor in the component A is at least one selected from carboxylic ester compounds, ether compounds, 1, 3-alcohol ester compounds and sulfonamide compounds;
the organic aluminum is aluminum hydroxide having AlRnX(3-n)An alkylaluminum compound of the structure and/or an alkylaluminoxane, R is C1-C20Alkyl radical, C7-C20Aralkyl or C6-C20Aryl, X is halogen, and n is an integer of 0 to 3; preferably, the compound has AlRnX(3-n)An alkylaluminum compound of structure (la) selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-butylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, dimethylaluminum monochloride, diisobutylaluminum monochloride, isobutylaluminum dichloride, tris (2-methyl-3-phenyl-butyl) aluminum and tris (2-phenyl-butyl) aluminum; preferably, the alkylaluminoxane is selected from methylaluminoxane, tetra (isobutyl) aluminoxane, tetra (2,4, 4-trimethyl-pentyl) aluminoxane, tetra (2, 3-dimethylbutyl) aluminumAt least one of an alkylene oxide and tetrakis (2,3, 3-trimethylbutyl) aluminoxane;
the external electron donor is at least one selected from siloxane compounds, amino silane compounds, organic amine compounds and ether compounds; preferably, the siloxane compound is selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, methyl-t-butyldimethoxysilane, cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, dicyclopentyldimethoxysilane, isobutylcyclohexyldimethoxysilane, tetraethoxysilane and n-propenotriethoxysilane; preferably, the aminosilane compound is selected from at least one of diethylaminotriethoxysilane, 3-aminopropyltriethoxysilane, diethylaminomethyltriethoxysilane, dimethylaminomethyltriethoxysilane, diisopropylaminomethyltriethoxysilane, di-n-propylaminomethyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, piperidinyltriethoxysilane, and pyrrolyltriethoxysilane; preferably, the organic amine compound is selected from the group consisting of aziridine, azetidine, pyrrolidine, azepane, azocane, 2, 3-dimethyl aziridine, 2,3, 3-tetramethyl aziridine, 2,4, 4-tetramethyl azetidine, 2,4, 4-tetraethylazetidine, 2,3, 3-tetramethyl azetidine, 2,3, 3-tetraethylazetidine, 2,4, 4-tetramethyl pyrrolidine, 2,5, 5-tetraethylpyrrolidine, 2,5, 5-tetra-n-propyl pyrrolidine, 2,5, 5-tetraisopropyl pyrrolidine, 2,2,5, 5-tetraisobutylpyrrolidine, 2,6, 6-tetramethylpiperidine, 2,6, 6-tetraethylpiperidine, 2,6, 6-tetra-n-propylpiperidine, 2,6, 6-tetraisopropylpiperidine, 2,6, 6-tetraisobutylpiperidine, 2,4, 4-tetramethylpiperidine, 2,4, 4-tetraethylpiperidine, 2,5, 5-tetramethylpiperidine, 2,5, 5-tetraethylpiperidine, 2-methyl-2-cyclohexyl-6-methyl-6-ethylpiperidine, 2-dicyclopentyl-6, 6-dimethylpiperidine, 2,7, 7-tetramethylazepane, 2,7, 7-tetraethylazepane, 2,2,7, 7-tetra-n-propylazepane, 2,7, 7-tetraisopropyl azepane, 2,7, 7-tetraisobutyl azepane, 2,5, 5-tetramethylazepane, 2,5, 5-tetraethylazepane, 3,5, 5-tetramethylazepane, 3,5, 5-tetraethylazepane, 2-methyl-2-cyclohexyl-7-methyl-7-azepane, 2-dicyclopentyl-7, 7-dimethylazepane, 2,8, 8-tetramethylazocane, 2,8, 8-tetraethylazocane, 2,8, 8-tetra-n-propylazocane, At least one of 2,2,8, 8-tetraisopropyl azocane, 2,8, 8-tetra-n-butyl azocane, 2,8, 8-tetraisobutyl azocane, 2,7, 7-tetramethyl azocane, 2,6, 6-tetramethyl azocane, 3,5, 5-tetramethyl azocane and 3,3,6, 6-tetramethyl azocane; preferably, the ether compound is selected from at least one of the compounds of the following formula:
wherein R is1And R2Each independently selected from C1-C20One of linear, branched or cyclic aliphatic radicals, R3、R4、R5、R6、R7And R8Each independently selected from a hydrogen atom, a halogen atom, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl and C7-C20One of aralkyl, and R3、R4、R5、R6、R7And R8Optionally linked to form a ring between any two of them; preferably, the ether compound is selected from the group consisting of 2, 2-diisobutyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2-benzyl-1, 3-dimethoxypropane, 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isopropyl-2-3, 7-dimethyloctyl-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1, 3-dimethoxypropane, 2-isopropyl-2-dimethylhexyl-1, 3-dimethoxypropane, and,2, 2-diisobutyl-1, 3-diethoxypropane, 2-diisobutyl-1, 3-dipropoxypropane, 2-isopropyl-2-isoamyl-1, 3-diethoxypropane, 2-isopropyl-2-isoamyl-1, 3-dipropoxypropane and 2, 2-bis (cyclohexylmethyl) -1, 3-diethoxypropane.
10. A flexible 1-butene polymer obtainable by the process according to any one of claims 4 to 9.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4533705A (en) * | 1980-01-17 | 1985-08-06 | Chisso Corporation | Process for producing α-olefin polymers |
| EP0186287A2 (en) * | 1984-11-01 | 1986-07-02 | Mitsui Petrochemical Industries, Ltd. | Random 1-butene copolymer |
| US4603184A (en) * | 1981-07-23 | 1986-07-29 | Chisso Corporation | Process for producing alpha-olefin polymers |
| EP0302297A1 (en) * | 1987-07-20 | 1989-02-08 | Idemitsu Petrochemical Co. Ltd. | Butene-1 copolymer |
| EP0419874A2 (en) * | 1989-08-30 | 1991-04-03 | Idemitsu Petrochemical Company Limited | Composition of polybutene-1 and process for preparing same |
| US5986021A (en) * | 1995-05-02 | 1999-11-16 | Borealis A/S | Process for manufacturing LLDPE polymers |
| US20090137753A1 (en) * | 2005-09-02 | 2009-05-28 | Borealis Technology Oy | Process for polymerizing olefins in the presence of an olefin polymerization catalyst |
| KR20140021698A (en) * | 2014-02-05 | 2014-02-20 | 주식회사 엘지화학 | Method for manufacturing polybutene-1 homopolymer or copolymer |
| CN103772557A (en) * | 2012-10-26 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method for high isotactic polybutene-1 |
-
2018
- 2018-10-23 CN CN201811238221.7A patent/CN111087509B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4533705A (en) * | 1980-01-17 | 1985-08-06 | Chisso Corporation | Process for producing α-olefin polymers |
| US4603184A (en) * | 1981-07-23 | 1986-07-29 | Chisso Corporation | Process for producing alpha-olefin polymers |
| EP0186287A2 (en) * | 1984-11-01 | 1986-07-02 | Mitsui Petrochemical Industries, Ltd. | Random 1-butene copolymer |
| EP0302297A1 (en) * | 1987-07-20 | 1989-02-08 | Idemitsu Petrochemical Co. Ltd. | Butene-1 copolymer |
| EP0419874A2 (en) * | 1989-08-30 | 1991-04-03 | Idemitsu Petrochemical Company Limited | Composition of polybutene-1 and process for preparing same |
| US5986021A (en) * | 1995-05-02 | 1999-11-16 | Borealis A/S | Process for manufacturing LLDPE polymers |
| US20090137753A1 (en) * | 2005-09-02 | 2009-05-28 | Borealis Technology Oy | Process for polymerizing olefins in the presence of an olefin polymerization catalyst |
| CN103772557A (en) * | 2012-10-26 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method for high isotactic polybutene-1 |
| KR20140021698A (en) * | 2014-02-05 | 2014-02-20 | 주식회사 엘지화학 | Method for manufacturing polybutene-1 homopolymer or copolymer |
Non-Patent Citations (1)
| Title |
|---|
| 孙宝余等: "高等规聚丁烯-1合成工艺研究进展", 《高分子通报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115073634A (en) * | 2021-03-16 | 2022-09-20 | 中国石油化工股份有限公司 | Process for producing poly-1-butene and poly-1-butene |
| CN115073634B (en) * | 2021-03-16 | 2024-03-01 | 中国石油化工股份有限公司 | Process for producing poly-1-butene and poly-1-butene |
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