CN111087503B - 1-butene polymer and slurry polymerization method of 1-butene - Google Patents
1-butene polymer and slurry polymerization method of 1-butene Download PDFInfo
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Abstract
The invention belongs to the field of olefin polymerization, and discloses a 1-butene polymer and a slurry polymerization method of 1-butene. The 1-butene slurry polymerization process comprises: 1-butene and optionally alpha-olefins are subjected to a slurry polymerization reaction in the presence of a Ziegler-Natta catalytic system, using liquid propane as solvent. The 1-butene slurry polymerization method provided by the invention takes liquid propane as a solvent, not only can effectively solve the problem of low polymerization activity and stickiness of a polymerization system caused by the fact that a polymer is dissolved in the solvent under high-temperature polymerization conditions, but also the obtained 1-butene polymer has high isotacticity, low total Volatile Organic Compound (VOC) content and good particle morphology. In addition, the 1-butene slurry polymerization method provided by the invention has simple process, and the subsequent polymer separation process is simple, thereby being convenient for industrial production.
Description
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to a 1-butene polymer and a 1-butene slurry polymerization method.
Background
As is well known, 1-butene polymers are widely used for pipes, such as hot water pipes, water supply pipes, industrial pipes, and building pipes, because of their great advantages in creep resistance, environmental cracking resistance, and impact resistance. The introduction of alpha-olefin (ethylene, propylene and the like) into the 1-butene polymer can obviously improve the performance of the 1-butene polymer, expand the application range, ensure that the 1-butene polymer has excellent easy tearing performance and the like, can obviously reduce the heat sealing initial temperature, is suitable for the field of film production, and is widely applied to the fields of food, sanitary product packaging and the like.
At present, the production methods of 1-butene polymers are mainly gas phase, solution and bulk methods, wherein the bulk method includes slurry bulk and liquid bulk methods.
The gas phase process usually adopts fluidized bed gas phase reactors, CN102040693, CN1140545C, US4503203, US3168484, US3580898, US5241024 and US3922322 all relate to the synthesis of 1-butene polymer with good particle morphology, controllable melt mass flow rate in a certain range and high isotactic index by directly reacting 1-butene monomer in a gas fluidized bed under the action of a Ziegler-Natta catalyst. However, the gas phase method has low monomer concentration and low 1-butene monomer partial pressure, which results in low polymerization activity (less than 5.0 KgPB/g. Cat), high ash content in the polymer and high catalyst requirement by adopting the gas phase method.
In US5037908 and US3944529, an inert solvent isobutane is used as a solvent to realize suspension polymerization of butene-1, so that a reaction is realized at a high temperature, and a granular butene-1 polymer with an isotactic index of more than 94% is obtained, but the butene-1 polymer can be swelled or dissolved in isobutane at a temperature of more than 45 ℃, so that the polymerization efficiency is low, the polymerization activity is low, the polymer ash content is high, the boiling points of butene-1 and isobutane are not greatly different (the difference is 0.6 ℃), and the separation process is complex.
US5237013 and CN103304709 use inert solvent n-hexane as diluent to realize solution polymerization of 1-butene, and the generated 1-butene polymer is precipitated or dissolved in the solvent, the method has the advantages of simple operation, easy derivation of polymerization heat from the system, convenient reaction control and the like, but the 1-butene polymer can be swelled or dissolved in the n-hexane solvent at higher temperature, so that the polymer form is uncontrollable, the concentration of 1-butene monomer in the n-hexane solvent is low, the polymerization rate and the polymerization activity are both low, and the equipment production capacity and the utilization rate are not high.
The excessive 1-butylene monomer is used as the solvent, so that the problems of inert solvent and monomer separation in the later reaction period can be avoided, and the conditions of complicated process and high cost caused by separation are solved. EP187034A2, US3944529, US6306996, CN103788262A and CN03800736.3 disclose that bulk polymerization can be carried out at 70-75 ℃ using a Ziegler-Natta catalyst system, the polymerization activity can reach 25kgPB/g cat h, and the polymer isotacticity index can reach 99%. However, although these methods have high reactivity and the obtained polymer has a high isotactic index, when the polymerization temperature is higher than 30 ℃, the 1-butene polymer is dissolved in 1-butene, which causes problems such as stickiness of the polymerization system, no granular form of the polymerization product, difficulty in discharging, and the like, and further, the post-treatment processing of the polymer is complicated.
CN101020728A, CN100488994C, CN103288993B, CN103897080A, CN 103772557A and CN200710013587 disclose that bulk slurry polymerization is carried out at a temperature of below 35 ℃ by adopting a Ziegler-Natta catalyst system, the polymerization activity is 6 kgPB/g. Cat, the polymer isotactic index can reach more than 98%, the polymer particle shape is good, the discharging is convenient, and the operation is simple.
In view of the above disadvantages of the prior art, there is still a need to develop a method for preparing 1-butene polymer, which can obtain 1-butene polymer with good particle morphology and high isotactic index and can solve the problems of low polymerization activity, sticky polymerization system and difficult transportation.
Disclosure of Invention
The present invention aims to provide a 1-butene polymer and a slurry polymerization method of 1-butene, which can solve the problems of low polymerization activity, sticky polymerization system and difficult transportation, and can obtain the 1-butene polymer with good particle shape and high isotactic index.
Specifically, the invention provides a 1-butene slurry polymerization method, wherein the method comprises the following steps: slurry polymerization of 1-butene and optionally alpha-olefin in the presence of a Ziegler-Natta catalyst system in liquid propane as solvent; the alpha-olefin is mono-olefin with double bonds of 2-10 carbon atoms at the end of the molecular chain except 1-butene.
In addition, the invention also provides the 1-butene polymer prepared by the method.
The 1-butene slurry polymerization method provided by the invention takes liquid propane as a solvent, not only can effectively solve the problem of low polymerization activity and stickiness of a polymerization system caused by the fact that a polymer is dissolved in the solvent under high-temperature polymerization conditions, but also the obtained 1-butene polymer has high isotacticity, low total Volatile Organic Compound (VOC) content and good particle morphology. In addition, the 1-butene slurry polymerization method provided by the invention has simple process, simple separation of subsequent polymers and convenience for industrial production.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a morphology of the polymer prepared in example 1;
FIG. 2 is a morphology of the polymer made by comparative example 2;
FIGS. 3 and 4 are morphology diagrams of polymers prepared by comparative example 1; wherein, FIG. 3 is a polymer morphology chart obtained by directly discharging after the temperature is reduced to below 30 ℃ after the polymerization is finished; FIG. 4 is a diagram showing the morphology of the polymer after the solvent has evaporated.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below.
The invention provides a 1-butene slurry polymerization method, which comprises the following steps: slurry polymerization of 1-butene and optionally alpha-olefins in the presence of a Ziegler-Natta catalyst system, using liquid propane as solvent; the alpha-olefin is a monoolefin having a double bond of 2 to 10 carbon atoms at the end of the molecular chain other than 1-butene, preferably ethylene and/or propylene. The boiling point difference between the 1-butene and the liquid propane is large, the separation in the industrial production process is convenient, and the removal of volatile components such as oligomer in the polymerization product is very favorable 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 reaction uses liquid propane as a solvent, in order to obtain a 1-butene polymer having higher isotacticity, lower VOC content and better particle morphology, it is preferred that the amount of liquid propane is 1 to 10mol, more preferably 2 to 9mol, most preferably 3 to 6mol, relative to 1mol of 1-butene.
According to the present invention, preferably, the conditions of the slurry polymerization include a temperature of 20 to 100 deg.C, more preferably 30 to 80 deg.C, a pressure of 0.1 to 5MPa, more preferably 0.1 to 3MPa, and a time of 0.1 to 5 hours, more preferably 0.5 to 2 hours. In the present invention, the pressures are gauge pressures.
The slurry polymerization reaction may be carried out in a single reactor, multiple series reactors, or multiple parallel reactors. The reactor can be a loop reactor, a vertical stirred tank reactor, or a combination of the above two. The slurry polymerization may be a continuous reaction or a batch reaction.
In the present invention, the α -olefin is an α -olefin having 2 to 10 carbon atoms other than 1-butene, and is preferably ethylene and/or propylene. In the slurry polymerization process, the α -olefin may be selectively used, and preferably, 1-butene is used in an amount of 90 to 100mol% and the α -olefin is used in an amount of 0 to 10mol%. When only 1-butene is used as a monomer in the slurry polymerization process, the obtained 1-butene polymer is a 1-butene homopolymer; when 1-butene and alpha-olefin are used as monomers simultaneously in the slurry polymerization process, the resulting 1-butene polymer is a copolymer of 1-butene and alpha-olefin.
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, CN106543310, CN106554439, CN107522800, CN107522803.
The internal electron donor in the component A can be selected from at least one of carboxylic ester compounds, ether compounds, 1,3-alcohol ester compounds and sulfonamide compounds, preferably at least one of phthalate compounds, 1,3-diether compounds, glycol ester compounds and succinate compounds, and most preferably 1,3-diether compounds.
The organoaluminum is preferably AlR n X (3-n) An alkylaluminum compound of the structure and/or an alkylaluminoxane, R is C 1 -C 20 Alkyl radical, C 7 -C 20 Aralkyl or C 6 -C 20 Aryl, X is halogen, and n is an integer of 0 to 3. Wherein the compound has AlR n X (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 alkyl aluminoxanePreferably 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 organoamine compound is preferably selected from the group consisting of aziridine, azetidine, pyrrolidine, azepane, azocane, -dimethylazepane, -tetramethylaziridine, -tetramethylazetidine, -tetraethylazetidine, -tetramethylazetidine, -tetramethylpyrrolidine, -tetraethylpyrrolidine, -tetra-n-propylpyrrolidine, -tetraisopropylpyrrolidine, -tetraisobutylpyrrolidine, -tetramethylpiperidine, -tetraethylpiperidine, -tetra-n-propylpiperidine, -tetraisopropylpiperidine, and-tetraisobutylpiperidine, -tetramethylpiperidine, -tetraethylpiperidine, 2-methyl-2-cyclohexyl-6-methyl-6-ethylpiperidine, -dicyclopentyl-dimethylpiperidine, -tetramethylazepane, -tetraethylazepane, -tetra-n-propylazepane, -tetraisopropylazepane, -tetraisobutylazepane, -tetramethylazepane, -tetraethylazepane, -tetramethylazepane, -tetraethylazepane, -2-methyl-2-cyclohexyl-7-methyl-7-azepane, -dicyclopentyl-dimethylazepane, 2,2,8,8-tetramethylazocane, 2,2,8,8-tetraethylazocane, 2,2,8,8-tetra-n-propylazocane, 2,2,8,8-tetraisopropyl azocane, 2,2,8,8-tetra-n-butyl azocane, 2,2,8,8-tetraisobutyl azocane, 2,2,7,7-tetramethylazocane, 2,2,6,6-tetramethylazocane, 3,3,5,5-tetramethylazocane, and 3,3,6,6-tetramethylazocane. The ether compound is preferably at least one selected from the group consisting of compounds of the following general formula:
wherein R is 1 And R 2 Each independently selected from C 1 -C 20 One of linear, branched or cyclic aliphatic radicals, R 3 、R 4 、R 5 、R 6 、R 7 And R 8 Each independently selected from a hydrogen atom, a halogen atom, C 1 -C 20 Straight or branched alkyl of (2), C 3 -C 20 Cycloalkyl radical, C 6 -C 20 Aryl radical, C 7 -C 20 Alkylaryl and C 7 -C 20 One of aralkyl radicals, and R 3 、R 4 、R 5 、R 6 、R 7 And R 8 Optionally linked to form a ring. Specific examples of the ether compound include, but are not limited to: 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-phenyl-1,3-dimethoxypropane, 2,2-benzyl-1,3-dimethoxypropane, 2-isopropyl-2-isoamyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropaneAt least one of 2-isopropyl-2-3,7-dimethyloctyl-dimethoxypropane, 2,2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,2-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 2,2-bis (cyclohexylmethyl) -1,3-diethoxypropane.
According to the invention, in the slurry polymerization process, a chain transfer agent is generally adopted to regulate the molecular weight of the polymer, namely hydrogen is added into a reaction system as a molecular weight regulator in different proportions; 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 1MPa.
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 a 1-butene polymer prepared by the polymerization method.
The 1-butene polymer prepared by the polymerization method provided by the invention has the following characteristics:
-has a melt mass flow rate (190 ℃,2.16 kg) of 0.1-100g/10 min;
-having an isotactic index greater than 95% by weight;
-having more than 85% isotactic pentads;
has a density of not less than 0.35g/cm 3 The bulk density of (a);
-has a drop time of less than 12 s;
-having a total volatile organic content lower than 50 μ g · C/g, preferably lower than 40 μ g · C/g.
The 1-butene polymer may be subjected to extrusion granulation, and additives conventionally used in the art, such as at least one of an antioxidant, a light stabilizer, a heat stabilizer, a colorant, and a filler, may be added during the granulation.
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, mgCl 2 /TiCl 4 The supported Ziegler-Natta catalyst is prepared by the following method: 200mL of white oil, 8.0g (0.08 mol) of magnesium chloride, 3g (0.01 mol) of octadecanol, 95mL (1.6 mol) of ethanol and 9.8mL (0.08 mol) of 2,2-dimethoxypropane are put into a 1.6L reaction kettle, and the temperature is raised to 90 ℃ under stirring; after reacting for 1 hour at constant temperature, dispersing the mixture for 30 minutes by stirring at low speed (the stirring speed is 400 revolutions per minute) to emulsify; adding 35mL (0.45 mol) 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; adding 100mL of titanium tetrachloride into a 300mL glass reaction bottle, cooling to-20 ℃, adding 8 g of the magnesium-containing carrier Z1, stirring at-20 ℃ for 30min, then slowly raising the temperature to 110 ℃, adding 1.5mL of diisobutyl phthalate in the process of raising the temperature, filtering the liquid after maintaining at 110 ℃ for 30min, then adding titanium tetrachloride and washing for 2 times to obtain a solid product, adding 100mL of titanium tetrachloride into the solid product, reacting at 25 ℃ for 16 h, finally washing for 4 times with hexane, and drying to obtain MgCl 2 /TiCl 4 A 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: 2.16911 kg,190 ℃.
(2) Molecular weight distribution M w /M n : measured by Waters GPC 2000, wherein the mass concentration of the sample is 0.1mg/mL, the measurement temperature is 150 ℃, the measurement flow rate is 1mL/min, a standard curve is prepared by taking the molecular weight of polystyrene as an internal reference, and the weight average molecular weight (M) of the sample is calculated from the flow-out time w ) Number average molecular weight (M) n ) And molecular weight distribution (M) w /M n )。
(3) Isotactic index (i.i.): weighing 3g of polymer, oven-treating to constant weight, and weighing m 1 Extracting with diethyl ether for 48h in a Soxhlet extractor, and recording the mass m of the polymer dried to constant weight 2 M, weight percentage of insoluble matter after ether extraction 2 /m 1 Namely the isotactic index of the polymer.
(4) Bulk density: the mass of 1-butene polymer per unit volume fell freely in the funnel filling the cylinder.
(5) The falling time is as follows: 100ml of polymer are introduced into a funnel of specific geometry and size for determining the bulk density of the powder, the time required for the powder to flow completely is recorded and the average is taken 3 times of tests.
(6) VOC measurement: the polymer powder was weighed using the German automobile industry Association VDA277 test standard.
(7) 13 C-NMR measurement: 120 ℃ in a deuterated o-dichlorobenzene solution of polymer (8-12 wt.%), by using a 90 ° pulse, a 15s delay between pulse and CPD to remove 1 H- 13 C 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-13NMR spectral analysis of stationary polymeric shifts and the polymerization mechanism.
Example 1
Air and trace water in a polymerization reaction kettle are removed at 75 ℃ in advance before reaction, and 3ml of triethyl aluminum with the concentration of 1mol/L and 3ml of triethyl aluminum with the concentration of 0.1mol are added into the reaction kettle (a vertical stirred tank reactor) under the protection of nitrogenL/L dicyclopentyldimethoxysilane and 10mg MgCl 2 /TiCl 4 The supported Ziegler-Natta catalyst was reacted at a polymerization temperature of 70 ℃ and a pressure of 2.0MPa for 1 hour by introducing 0.2MPa of hydrogen and adding 1.5L of a propane solution while controlling the stirring speed at 400rpm/min, and then introducing 1.2L of a 1-butene monomer (4 mol of liquid propane relative to 1mol of 1-butene) into the reactor. After the reaction is finished, the pressure in the kettle is reduced to be below 0.5MPa, the polymer is discharged into a device containing hot water, the polymer is fully contacted with the water, the polymer is dried, weighed and subjected to characterization analysis, and the analysis result of the polymer is shown in Table 1.
Example 2
The catalyst and polymerization process conditions used in example 2 were the same as in example 1. The difference from the embodiment 1 is that: no hydrogen is added in the initial stage of the reaction, after 1 hour of the reaction, 0.5MPa of hydrogen is introduced into the reaction kettle to continue the reaction for 0.5 hour, and the analysis results of the obtained polymer are listed in Table 1.
Example 3
The catalyst and polymerization process conditions used in example 3 were the same as in example 1. The difference from the embodiment 1 is that: the hydrogen partial pressure in the reaction vessel was changed to 1.0MPa, and the analysis results of the obtained polymer are shown in Table 1.
Example 4
The catalyst and polymerization process conditions used in example 4 were the same as in example 1. The difference from the embodiment 1 is that: the reaction monomer was a mixture of 1-butene and ethylene, wherein the ethylene content was 0.3mol%, and the analysis results of the obtained polymer are shown in Table 1.
Example 5
The catalyst and polymerization process conditions used in example 5 were the same as in example 1. The difference from the embodiment 1 is that: the reaction monomer was a mixture of 1-butene and propylene, wherein the propylene content was 0.2mol%, and the analytical results of the obtained polymer are shown in Table 1.
Comparative example 1
Unlike example 1, the polymerization was carried out using hexane as a reaction solvent. Removing air and trace water in a polymerization reaction kettle at 75 ℃ in advance before reaction, and adding the mixture into the reaction kettle under the protection of nitrogen3ml of triethylaluminum at a concentration of 1mol/L, 3ml of dicyclopentyldimethoxysilane at a concentration of 0.1mol/L and 10mg of MgCl 2 /TiCl 4 The supported Ziegler-Natta catalyst is added with 0.2MPa hydrogen and 1.5L of hexane solution, the stirring speed is controlled at 400rpm/min, then 1.2L of 1-butene monomer is added into the reaction kettle, and the reaction is carried out for 1h at the polymerization temperature of 70 ℃ and the pressure of 2.0 MPa. After the reaction is finished, the polymerization temperature is reduced to below 30 ℃, the polymer solution is collected, after the inert solvent is completely volatilized, the polymer solution is placed in a vacuum oven to be dried, weighing and characterization analysis are carried out, and the analysis results of the polymer are listed in table 1.
Comparative example 2
Comparative example 2 the reaction was carried out using a bulk preparation process. Air and trace water in a polymerization reaction kettle are removed at 75 ℃ in advance before reaction, and 3ml of triethyl aluminum with the concentration of 1mol/L, 3ml of dicyclopentyldimethoxysilane with the concentration of 0.1mol/L and 10mg of MgCl are added into the reaction kettle under the protection of nitrogen 2 /TiCl 4 The supported Ziegler-Natta catalyst is added with 0.2MPa hydrogen and 2.5L 1-butylene monomer, the stirring speed is controlled at 400rpm/min, and the reaction is carried out for 1h at the polymerization temperature of 70 ℃ and the pressure of 2.0 MPa. After the reaction is finished, the pressure in the kettle is reduced to be below 0.5MPa, the polymer is discharged into a device containing hot water, the polymer is fully contacted with the water, the polymer is dried, weighed and subjected to characterization analysis, and the analysis result of the polymer is shown in Table 1.
As can be seen from the results in Table 1, the slurry polymerization method of butene-1 provided by the present invention can obtain higher polymerization activity, and the obtained butene-1 polymer also has higher isotacticity, lower total Volatile Organic Compound (VOC) content and better particle morphology.
Further, the morphology of the polymer obtained in example 1 is shown in FIG. 1, the morphology of the polymer obtained in comparative example 2 is shown in FIG. 2, and the morphology of the polymer obtained in comparative example 1 is shown in FIGS. 3 and 4 (wherein, FIG. 3 is a graph showing the morphology of the polymer obtained by directly discharging the polymer after the completion of polymerization by lowering the temperature to 30 ℃ or lower, and FIG. 4 is a graph showing the morphology of the polymer after the completion of solvent evaporation). As can be seen from FIGS. 1 to 4, the polymer particles obtained by the process of the present invention have regular morphology; after the high-temperature polymerization is finished and the pressure in the kettle is reduced, the polymer is in an irregular blocky structure; the polymer obtained by using hexane as a solvent is directly discharged to be viscous after the temperature is reduced to be below 30 ℃ after the polymerization is finished, and the polymer obtained after the solvent is volatilized is extremely irregular in shape. In conclusion, the method provided by the invention can control the polymer form in the olefin polymerization reaction, and solves the problems that the polymer form and the system stickiness cannot be controlled in the bulk method and the conventional solution method (using non-liquid propane as a solvent).
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 1-butene slurry polymerization process comprising: slurry polymerization of 1-butene and optionally alpha-olefins in the presence of a Ziegler-Natta catalyst system, using liquid propane as solvent; the alpha-olefin is mono-olefin with double bonds of 2-10 carbon atoms at the end of a molecular chain except 1-butene;
the amount of liquid propane is 3 to 6mol relative to 1mol of 1-butene;
the slurry polymerization is carried out in the presence of hydrogen, and the partial pressure of hydrogen is 0.5-1MPa;
the reaction temperature of the slurry polymerization reaction is 70-100 ℃;
the Ziegler-Natta catalyst system comprises a component A, a component B and a component C, wherein the component A is a Ziegler-Natta catalyst which is loaded by magnesium chloride, contains Ti and contains an internal electron donor, the component B is organic aluminum, and the component C is an external electron donor; the internal electron donor is a phthalate compound; the external electron donor is dicyclopentyldimethoxysilane.
2. The slurry polymerization process of 1-butene according to claim 1, wherein the conditions of the slurry polymerization reaction comprise a pressure of 2 to 5MPa and a time of 0.1 to 5 hours.
3. The slurry polymerization process of 1-butene according to claim 1, wherein the slurry polymerization is carried out in a loop reactor or a vertical stirred tank reactor.
4. The slurry polymerization process of 1-butene according to claim 1, wherein the 1-butene is used in an amount of 90 to 100mol% and the α -olefin is used in an amount of 0 to 10mol%.
5. The 1-butene slurry polymerization process according to claim 1, wherein the molar ratio of component A to component B is 1 (10-500) in terms of titanium/aluminum; the molar ratio of the component C to the component B is (0.005-0.5): 1.
6. The slurry polymerization process of 1-butene according to claim 5, wherein the molar ratio of component A to component B is 1 (25-100) in terms of titanium/aluminum, and the molar ratio of component C to component B is (0.01-0.4) to 1.
7. The butene-1 slurry polymerization process according to claim 1,
the organic aluminum is aluminum hydroxide having AlR n X (3-n) An alkylaluminum compound of the structure and/or an alkylaluminoxane, R is C 1 -C 20 Alkyl radical, C 7 -C 20 Aralkyl or C 6 -C 20 Aryl, X is halogen, and n is an integer of 0 to 3.
8. The 1-butene slurry polymerization process of claim 7, wherein the alrs are present n X (3-n) The alkyl aluminum compound with the structure is selected from trimethyl aluminum, triethyl aluminum and triisoAt least one of butylaluminum, 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.
9. The 1-butene slurry polymerization process according to claim 7, wherein the alkylaluminoxane is selected from at least one of methylaluminoxane, tetra (isobutyl) aluminoxane, tetra (2,4,4-trimethyl-pentyl) aluminoxane, tetra (2,3-dimethylbutyl) aluminoxane and tetra (2,3,3-trimethylbutyl) aluminoxane.
10. 1-butene polymer obtainable by a slurry polymerization process of 1-butene according to any one of claims 1 to 9.
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