CN112759685B - Catalyst component for ethylene polymerization reaction, preparation method thereof, catalyst and application thereof - Google Patents
Catalyst component for ethylene polymerization reaction, preparation method thereof, catalyst and application thereof Download PDFInfo
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Abstract
The invention provides a catalyst component for ethylene polymerization reaction, a preparation method thereof, a catalyst and application thereof. The catalyst component comprises the reaction product of: magnesium compounds, oxygen-containing titanium compounds, organic epoxy compounds, alcohol ether compounds, ether compounds and halogenating agents. The invention can form completely soluble magnesium-titanium complex uniform solution in nonpolar solvent at lower temperature, thus reducing energy consumption; the obtained powder is spherical particles, the dispersibility is good, and the bulk density of the powder obtained by polymerization is higher.
Description
Technical Field
The invention relates to the field of catalysts for olefin polymerization, in particular to a catalyst component for ethylene polymerization reaction, a preparation method thereof, a catalyst for ethylene polymerization reaction and application thereof.
Background
With the development of ethylene polymerization process, the catalyst preparation technology matched with the polymerization process is also continuously improved, at present, the catalyst system of Ti/Mg compound occupies a dominant position in the industrial production of polyethylene, and the main concerned technical indexes comprise the polymerization activity, hydrogen regulation sensitivity, copolymerization performance, particle morphology and particle size distribution of the catalyst and the like. The control of catalyst particle shape, surface structure, particle size and particle size distribution are important indexes for polyolefin industrial operation, the catalyst morphology affects parameters such as bulk density, flowability, particle adhesion of polymer powder, the polymer replicates the morphology of the catalyst, the poor catalyst morphology may cause the deterioration of the polymer morphology, which may cause fouling or sheeting of industrial equipment, so that a catalyst with good morphology control, desired particle size and morphology, narrow distribution, high bulk density and low adhesion is industrially required.
In order to control the particle form of the catalyst and obtain the catalyst with uniform and better particle form, scientific researchers adopt a dissolution and precipitation preparation method. For example, the Z-N catalyst is prepared by dissolving a magnesium compound or a complex of a magnesium compound and precipitating again, controlling a certain production condition, and preparing spheroidal Ti-MgCl 2 In patent CN1229092A, magnesium chloride is used as a carrier, titanium tetrachloride is used as an active component, and the preparation method of the catalyst is as follows: firstly MgCl 2 Dissolving in solvent system to form uniform transparent solution, and reacting with TiCl in the presence of benzoic anhydride at low temperature 4 The solid catalyst is precipitated by slowly raising the temperature. As organic matters such as phthalic anhydride and the like are needed to be used as a precipitation aid to promote precipitation during synthesis of the catalyst, and a large amount of titanium tetrachloride is needed to be added, the existence of anhydride can generate adverse effect on the catalyst, and simultaneously, a large amount of titanium tetrachloride can cause waste and pollution, and the system is easy to be sticky, so that the catalyst is difficult to prepare. In chinese patent CN1958620A, magnesium chloride is used as a carrier, titanium tetrachloride is used as an active component, and the preparation method of the catalyst is as follows: mgCl is first prepared 2 Dissolving in solvent system to form uniform transparent solution, and reacting with TiCl in the presence of silicone ester compound at low temperature 4 The solid catalyst is precipitated by slowly raising the temperature. The catalyst component obtainedWhen the catalyst is used for ethylene polymerization, the catalytic activity of the catalyst is higher, but the polymer particle shape is not ideal enough, especially the fluidity of the prepared polymer powder is not ideal, so that the catalyst still can not completely meet the requirement of industrial production when producing some resin with higher polymer powder fluidity requirement. Therefore, it is desirable to provide a catalyst suitable for ethylene polymerization process, which not only has higher catalytic activity and better hydrogen response, but also has good catalyst particle morphology and polymer particle morphology, especially the prepared polymer powder has better fluidity.
The preparation method of dissolution and precipitation is adopted by researchers, for example, the catalyst particles obtained in Chinese patents CN1158136A, CN1299375A and CN1795213A, US patents US3787384A, US4148754A, US4173547A and US4508843A have unsatisfactory particle morphology, wide distribution and even multimodal distribution, which are not beneficial to the long-period and stable operation of a polymerization device.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a catalyst component for ethylene polymerization reaction, a preparation method thereof, a catalyst for ethylene polymerization reaction and application thereof. The catalyst particles obtained by the invention are in a sphere-like shape, the adhesion of the catalyst particles is low, the catalyst particles have higher catalytic activity when being used for ethylene homopolymerization or copolymerization, and the prepared polymer powder has better fluidity and is suitable for producing special-brand resin in an ethylene slurry polymerization process.
One object of the present invention is to provide a catalyst component for ethylene polymerization comprising the reaction product of: magnesium compounds, oxygen-containing titanium compounds, organic epoxy compounds, alcohol ether compounds, ether compounds and halogenating agents.
The magnesium compound is Mg (OR) with a general formula (I) 1 ) m Cl 2-m In which R is 1 Is C 2 ～C 20 A saturated or unsaturated, linear or branched hydrocarbon radical, or is C 3 ～C 20 Saturated or unsaturated cycloalkyl, m is more than or equal to 0 and less than or equal to 2;
the oxygen-containing titanium compound is shown as the general formula(Ⅱ)Ti(OR 2 ) n Cl 4-n In which R is 2 Is C 2 ～C 20 A saturated or unsaturated, linear or branched hydrocarbon radical, or C 3 ～C 20 Saturated or unsaturated cyclic alkyl, n is more than 0 and less than or equal to 4;
the organic epoxy compound comprises at least one of oxide, glycidyl ether and internal ether of aliphatic olefin, diene or halogenated aliphatic olefin or diene with 2-8 carbon atoms, preferably at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether and diglycidyl ether, and more preferably at least one of epichlorohydrin or methyl glycidyl ether;
the alcohol ether compound is represented by the general formula (III) R 3 OR 4 OH, wherein R is 3 、R 4 Identical or different, each independently is C 2 ～C 20 A saturated or unsaturated, linear or branched hydrocarbon radical, or is C 3 ～C 20 A saturated or unsaturated cyclic hydrocarbon group;
the ether compound is at least one selected from anisole, phenetole, propyl ether, butyl ether, isopropyl ether, isobutyl ether, 1, 4-dioxane, tetrahydrofuran, ethylene oxide, 1, 2-propylene oxide, 1, 2-butylene oxide, cis-2, 3-butylene oxide, trans-2, 3-butylene oxide, 9- (bis (methoxymethyl) fluorene, isoamyl ether, amyl ether and the like.
The halogenating reagent is shown as a general formula (IV) R 5 a MX b Wherein M is a third, fourth or fifth main group element or a transition metal element, X is a halogen, R is a halogen atom 5 Is C 2 ～C 20 Saturated or unsaturated, linear or branched hydrocarbon radical, C 3 ～C 20 Saturated or unsaturated cycloalkyl or alkoxy radicals, C 6 ～C 20 Aromatic group, a =0, 1 or 2,b =1, 2,3 or 4.
According to the catalyst component provided by the present invention, preferably, in the general formula (I), R 1 Is C 2 ～C 10 Alkyl groups of (a); the magnesium compound is preferably selected from alkoxy magnesium compound and/or magnesium chlorideMore preferably at least one selected from diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, dioctoxymagnesium, and magnesium dichloride.
According to the catalyst component provided by the present invention, preferably, in the general formula (II), R 2 Is C 2 ～C 10 Alkyl groups of (a); the oxygen-containing titanium compound is preferably titanate, and more preferably at least one selected from tetrabutyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate and tetra-tert-butyl titanate.
According to the catalyst component provided by the present invention, preferably, in the general formula (III), R 3 、R 4 Is C 2 ～C 10 A saturated or unsaturated, linear or branched hydrocarbon radical, or C 3 ～C 10 A saturated or unsaturated cyclic hydrocarbon group; the alcohol ether compound is preferably selected from an ethylene glycol ether compound or a propylene glycol ether compound, and more preferably from at least one of 1-butoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, 1-methoxy-2-propanol, ethylene glycol monohexyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, and ethylene glycol monobutyl ether.
According to the catalyst component provided by the invention, preferably, in the general formula (IV), M is selected from aluminum, silicon or titanium, R 5 Is C 2 ～C 10 A saturated or unsaturated, linear or branched hydrocarbon radical, or C 3 ～C 10 A saturated or unsaturated cyclic hydrocarbon group; the halogenating agent is preferably TiCl 4 、R 6 n TiCl 4-n 、SiCl 4 、R 6 nSiCl 4-n 、R 6 n AlCl 4-n Wherein R is 6 Is C 2 ～C 20 Saturated or unsaturated, linear or branched hydrocarbon radical, C 3 ～C 20 Saturated or unsaturated cycloalkyl or alkoxy radicals, C 6 ～C 20 An aromatic radical, n is an integer of 0<n<4; more preferably, the halogenating agent is selected from ethylaluminum dichloride, diethylaluminum monochloride, isobutylaluminum dichloride, diisobutylaluminum monochloride, isopropylaluminum dichloride, diisopropylaluminum monochloride, silicon tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium monochlorotriethoxytitanium, diethoxyethylenedichlorideAt least one of titanium and titanium trichloroethoxy.
According to the catalyst component provided by the present invention, preferably, the oxygen-containing titanium compound is used in an amount of 0.1 to 20 moles, preferably 0.1 to 5.0 moles, more preferably 0.1 to 3.0 moles, per mole of magnesium in the magnesium compound; the organic epoxy compound is used in an amount of 0.1 to 10 moles, preferably 0.1 to 5.0 moles, more preferably 0.1 to 3.0 moles; the amount of the alcohol ether compound to be used is 0.1 to 10 mol, preferably 0.1 to 5.0 mol, more preferably 0.1 to 3.0 mol; the ether compound is used in an amount of 0.01 to 10 moles, preferably 0.05 to 5 moles, more preferably 0.1 to 3.0 moles; the amount of the halogenating agent to be used is 0.5 to 50 mol, preferably 0.5 to 20 mol, more preferably 5 to 20 mol.
Another object of the present invention is to provide a method for preparing a catalyst component for ethylene polymerization, comprising the steps of:
(1) Contacting a magnesium compound, an oxygen-containing titanium compound, an organic epoxy compound and an alcohol ether compound, and reacting to form a transparent solution;
(2) Contacting the solution obtained in the step (1) with a halogenating reagent, and reacting to obtain a suspension;
(3) Curing the suspension obtained in the step (2) to obtain the catalyst component;
wherein the ether compound is added in step (1), or added to the transparent solution obtained in step (1), or added in step (2), or added in step (3).
In the preparation method, in the step (1), the reaction temperature is 30-100 ℃, and preferably 40-80 ℃; the reaction time is 1 to 20 hours, preferably 4 to 10 hours;
in the step (2), the reaction temperature is-30 to 50 ℃, and preferably-30 to-10 ℃; the reaction time is 1min to 10 hours, preferably 0.5 to 5 hours;
in the step (3), the aging treatment time is 0.5 to 15 hours, preferably 1 to 12 hours.
According to a specific embodiment of the present invention, the method may include:
(a) Contacting a magnesium compound, an oxygen-containing titanium compound, an organic epoxy compound and an alcohol ether compound, and reacting to form a transparent solution of a magnesium-titanium complex;
(b) Contacting the transparent solution obtained in the step (a) with an ether compound, and reacting to obtain a homogeneous solution;
(c) Contacting the homogeneous solution obtained in the step (b) with a halogenating reagent, and reacting to obtain a suspension;
(d) Curing the suspension obtained in step (c) to obtain the catalyst component.
In the above embodiment according to the present invention, in the step (a), the magnesium compound, the oxygen-containing titanium compound, the organic epoxy compound and the alcohol ether compound are contacted with each other at 30 to 100 ℃, preferably at 40 to 80 ℃ to react to form a homogeneous transparent solution of the magnesium-titanium complex; the higher temperature favours the formation of a transparent solution of the magnesium titanium compound, the reaction is carried out under stirring conditions and the reaction time depends on the nature of the reactants and the operating conditions and is sufficient to obtain a transparent solution. The reaction time required is from 1 to 20 hours, preferably from 4 to 10 hours. An appropriate amount of inert diluent can be added as required to help the dispersion of the magnesium compound solution and reduce the viscosity of the solution, but the inert diluent cannot chemically react with the dissolved components; the inert diluent is a hydrocarbon, preferably at least one selected from the group consisting of hexane, cyclohexane, pentane, heptane, isobutane, isopentane, isooctane, and toluene.
In the step (b), the transparent solution obtained in the step (a) is contacted with an ether compound at the temperature of 0-100 ℃ for reaction, the reaction temperature is lower than the decomposition temperature of the magnesium-titanium complex and the ether compound, generally 0-100 ℃, and preferably 0-80 ℃; the mixing time is generally selected from 30 minutes to 6 hours, preferably from 1 to 4 hours. The ether compound may be added in the step (a) of preparing the transparent solution of the magnesium-titanium complex in the catalyst preparation process, thereby omitting the preparation process in the step (b), or may be added after the catalyst particles are precipitated and formed, or may be added to the catalyst suspension in the aging process.
Step (c), which may also be referred to as a precipitation step, comprises contacting the homogeneous solution obtained in step (b) with a halogenating agent to react and form a precipitate, to obtain a suspension of the catalyst component; in this step, chlorination or chlorination reduction of the magnesium-titanium complex is completed, that is, chlorine is substituted for alkoxy in the magnesium-titanium complex, and different halogenating agents can also reduce the valence of the oxygen-containing titanium compound to a lower valence, so that the active center group of the catalyst is precipitated out of the solution. The contacting of the transparent solution of magnesium-titanium complex with the halogenating agent may be carried out by any known suitable method, for example, by gradually adding the transparent solution of magnesium-titanium complex dropwise to the solution of halogenating agent, or by gradually adding the solution of halogenating agent dropwise to the transparent solution of magnesium-titanium complex. The dropping speed is usually controlled based on the local overheating which does not cause the reaction, and stirring is usually carried out during the dropping process to facilitate the smooth proceeding of the reaction. In the precipitation step, the reaction temperature may be controlled at-30 to 50 deg.C, preferably-30 to-10 deg.C. The reaction time of the precipitation step should be long enough to obtain complete precipitation, and the reaction time may be 1 minute to 10 hours, preferably 0.5 to 5 hours.
And (d) curing the suspension obtained in the step (c), standing, washing and drying to obtain the catalyst component.
After the precipitation step, the reaction is carried out for a period of time at a certain temperature, and then the aging treatment is carried out by heating, so that the particle shape of the catalyst is favorable, the particle size distribution of the catalyst can be narrowed to a certain extent, and the strength of the catalyst particles can be improved, thereby reducing the particle crushing phenomenon of the catalyst in the process of catalyzing ethylene polymerization. The temperature of the aging treatment is generally equal to or higher than the temperature of the precipitation reaction, and depends on the nature of the reactants, and the aging temperature is not higher than the boiling point or decomposition temperature of each component and inert diluent; the aging reaction time may be controlled to 0.5 to 15 hours, preferably 1 to 12 hours.
After the maturation treatment, washing is generally carried out to remove excess reactants and by-products formed during the preparation, and any inert solvent can be used in the washing step, for example at least one of toluene, isobutane, pentane, hexane, heptane and cyclohexane can be chosen, toluene or hexane being generally chosen as the inert solvent for washing in the experiments. After washing, the suspension of the catalyst component may be dried by purging with nitrogen under heating to obtain a powder of the catalyst component.
According to the catalyst component preparation method provided by the present invention, preferably, the oxygen-containing titanium compound is used in an amount of 0.1 to 20 moles, preferably 0.1 to 5.0 moles, per mole of magnesium in the magnesium compound; the amount of the organic epoxy compound used is 0.1 to 10 moles, preferably 0.1 to 5.0 moles; the amount of the alcohol ether compound is 0.1 to 10 moles, preferably 0.1 to 5.0 moles; the ether compound is used in an amount of 0.01 to 10 moles, preferably 0.05 to 5 moles; the halogenating agent is used in an amount of 0.5 to 50 mol, preferably 0.5 to 20 mol.
It is a further object of the present invention to provide a catalyst for ethylene polymerization comprising the reaction product of:
(A) The catalyst component for ethylene polymerization; or a catalyst component prepared by the preparation method;
(B) Is a general formula (IV) AlR p X 3-p An organoaluminum compound represented by the formula, wherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, p is an integer of 1<p≤3。
Among them, the component (B) may be used by mixing one or more kinds of alkylaluminums, and the organoaluminum compound is preferably selected from AlEt 3 、Al(iso-Bu) 3 、Al(n-C 6 H 13 ) 3 、Al(n-C 8 H 17 ) 3 And AlEt 2 At least one of Cl.
In the catalyst of the present invention, the molar ratio of aluminum in the organoaluminum compound to titanium in the catalyst component is an aluminum-titanium ratio generally used in the art as a catalyst, and is preferably 20 to 300, more preferably 30 to 260.
It is a fourth object of the present invention to provide a method for preparing the catalyst for ethylene polymerization, comprising the step of mixing and reacting the catalyst component and the organoaluminum compound.
The component (A) and the component (B) can be directly used in the polymerization reaction, or can be mixed for reaction and then applied to the polymerization reaction.
The fifth purpose of the invention is to provide the application of the catalyst in ethylene polymerization reaction.
The catalyst of the invention can be applied to ethylene homopolymerization and copolymerization of ethylene and other alpha-olefins.
The polymerization conditions are not particularly limited, and may be those commonly used in the art for olefin polymerization.
The alpha-olefin can be one of propylene, butene, pentene, hexene, octene and 4-methylpentene-1.
Through the technical scheme, the invention has the beneficial effects that: the completely soluble magnesium-titanium complex homogeneous solution can be formed in a nonpolar solvent at a lower temperature, the energy consumption is reduced, and the preparation process is simple; the catalyst of the invention is spherical particles while the activity of the catalyst is kept at a higher level, the adhesion of the catalyst particles is low, the dispersibility is better, the bulk density of powder obtained by the polymerization of the catalyst is higher, the particle size distribution of the catalyst is narrow, and the particle size distribution is more uniform.
Drawings
Fig. 1 shows a scanning electron micrograph of the catalyst obtained in comparative example 2.
Fig. 2 shows a scanning electron micrograph of the catalyst obtained in comparative example 1.
FIG. 3 shows a scanning electron micrograph of the catalyst obtained in example 1.
FIG. 4 shows a scanning electron micrograph of the catalyst obtained in example 5.
Fig. 5 shows a scanning electron micrograph of the catalyst obtained in comparative example 3.
FIG. 6 shows a scanning electron micrograph of the catalyst obtained in comparative example 4
Detailed Description
Preferred embodiments of the present invention will be described in more detail below by way of examples. While the examples describe preferred embodiments of the invention, it should be understood that the invention may be embodied in various forms and should not be construed as limited to the embodiments set forth herein.
The starting materials used in the embodiments of the present invention are commercially available.
The test method comprises the following steps:
the morphology of the catalyst is as follows: measured on a SL-30 field emission environment scanning electron microscope manufactured by FEI corporation of America;
the particle size distribution of the catalyst is as follows: a MASTERSIZE particle size distribution instrument, wherein n-hexane is used as a dispersing agent, and the measuring range is 0.02-2000 μm;
determination of bulk density: DIN-53194.
Example 1
(1) Weighing 0.037mol of magnesium dichloride, adding the magnesium dichloride into a glass reaction kettle, adding 0.038mol of tetrabutyl titanate into the glass reaction kettle, adding 0.038mol of epoxy chloropropane, 0.037mol of ethylene glycol monobutyl ether and 110 ml of toluene, heating to 60 ℃, stirring for 6 hours, and reacting until a transparent solution is formed;
(2) Adding 4.57mmol of tetrahydrofuran into the transparent solution obtained in the step (1), and stirring for 2 hours at 60 ℃ to react to obtain a homogeneous solution;
(3) Cooling the solution in the step (2) to-22 ℃, slowly dripping 0.4mol of titanium tetrachloride solution into the homogeneous solution obtained in the step (2) by using a constant-pressure dripping pipe, stirring and reacting at-22 ℃ for 1 hour after dripping is finished, heating to 10 ℃ within 30 minutes, reacting at 10 ℃ for 1 hour, heating to 90 ℃ within 2 hours, and stirring and reacting at 90 ℃ for 2 hours to obtain a suspension of a catalyst component;
(4) Cooling the suspension to 50 ℃, standing, settling, washing once with 80 ml of toluene, and washing three times with hexane, wherein the amount of hexane used in each time is 80 ml; after washing, the mixture is dried by blowing high-purity nitrogen at the bath temperature of 75 ℃ to obtain solid flowable powder.
Evaluation of catalyst: adding 1L of hexane, 1mmol of triethyl aluminum and 10mg of the catalyst components into a 2L stainless steel stirring kettle, then increasing the temperature to 80 ℃, adding 0.28MPa of hydrogen at one time, then maintaining the total pressure of the system at 0.73MPa by using ethylene for polymerization reaction, after reacting for 2 hours, stopping adding ethylene, cooling, relieving pressure, weighing polyethylene powder, and calculating the activity of the catalyst. The polyethylene powder was tested for bulk density and the results are shown in table 1 and the catalyst scanning electron microscopy results are shown in figure 3.
Example 2
A catalyst component was prepared according to the method of example 1, except that 4.57mmol of THF in step (2) was changed to 9.14mmol.
The catalyst was evaluated in the same manner as in example 1, and the polymerization results are shown in Table 1.
Example 3
A catalyst component was prepared by the method of example 1 except that 4.57mmol of THF in step (2) was changed to 3.66mmol of 9,9- (methoxymethyl) fluorene.
The catalyst was evaluated in the same manner as in example 1, and the polymerization results are shown in Table 1.
Example 4
A catalyst component was prepared by following the procedure of example 1 except that 110 ml of toluene in step (1) was changed to 150 ml.
The catalyst was evaluated in the same manner as in example 1, and the polymerization results are shown in Table 1.
Example 5
A catalyst component was prepared by the method of example 1, except that 4.57mmol of THF was charged into the reaction vessel in the step (1) and the step (2) was omitted. The catalyst was evaluated in the same manner as in example 1, and the polymerization results are shown in Table 1 and the results of the scanning electron microscope test of the catalyst are shown in FIG. 4.
Example 6
A catalyst component was prepared by following the procedure of example 1 except that the amount of epichlorohydrin added was changed from 0.038mol to 0.076mol.
The catalyst was evaluated in the same manner as in example 1, and the polymerization results are shown in Table 1.
Example 7
A catalyst component was prepared by following the procedure of example 1 except that the amount of ethylene glycol monobutyl ether added was changed from 0.037mol to 0.080mol.
The catalyst was evaluated in the same manner as in example 1, and the polymerization results are shown in Table 1.
Example 8
A catalyst component was prepared in the same manner as in example 1 except that the amount of tetrahydrofuran added was changed from 4.57mmol to 13.7mmol.
The catalyst was evaluated in the same manner as in example 1, and the polymerization results are shown in Table 1.
Comparative example 1
(1) Weighing 0.037mol of magnesium dichloride, adding the magnesium dichloride into a glass reaction kettle, adding 0.038mol of tetrabutyl titanate into the glass reaction kettle, adding 0.038mol of epoxy chloropropane, 0.037mol of ethylene glycol monobutyl ether and 110 ml of toluene, heating to 60 ℃, stirring, and reacting until a transparent solution is formed;
(2) Cooling the solution in the step (1) to-22 ℃, slowly dripping 0.4mol of titanium tetrachloride solution into the homogeneous solution obtained in the step (2) by using a constant-pressure liquid dripping pipe, after finishing dripping, stirring and reacting at-22 ℃ for 1 hour, heating to 10 ℃ within 30 minutes, reacting at 10 ℃ for 1 hour, then heating to 90 ℃ within 2 hours, and stirring and reacting at 90 ℃ for 2 hours to obtain a suspension of the catalyst component;
(3) Reducing the temperature of the suspension to 50 ℃, standing, settling, washing once with 80 ml of toluene, and washing three times with hexane, wherein the amount of hexane used in each time is 80 ml; after washing, the mixture is dried by blowing high-purity nitrogen at the bath temperature of 75 ℃ to obtain solid flowable powder. The catalyst was evaluated in the same manner as in example 1, and the polymerization results are shown in Table 1, and the results of the catalyst scanning electron microscope test are shown in FIG. 2.
Comparative example 2
(1) Weighing 1.0mol of diethoxymagnesium, adding 1.0mol of tetrabutyl titanate, stirring and dissolving at 140 ℃ until a transparent solution is formed, cooling the solution to room temperature, and adding 400 ml of dry hexane for dilution for later use;
(2) Weighing 9 ml of the transparent solution obtained in the step (1), slowly dropwise adding 15 ml of 3M ethyl aluminum dichloride hexane solution by using a burette, stirring and reacting for 4 hours at 60 ℃ after the dropwise adding is finished, and curing to obtain a catalyst component suspension.
(3) Cooling the suspension of the catalyst component to room temperature, standing, settling, and washing with hexane for three times, wherein the amount of hexane used in each time is 50 ml; after washing, the mixture is dried by blowing high-purity nitrogen at the bath temperature of 65 ℃ to obtain brown solid fluidity powder.
The catalyst was evaluated in the same manner as in example 1, and the polymerization results are shown in Table 1, and the results of the catalyst scanning electron microscope test are shown in FIG. 1.
Comparative example 3
(1) Weighing 0.037mol of magnesium dichloride, adding into a glass reaction kettle, adding 0.038mol of tetraethyl titanate, adding 0.038mol of epichlorohydrin, 0.076mol of ethanol and 110 ml of toluene, heating to 60 ℃, and stirring for reaction until a transparent solution is formed;
(2) Cooling the solution obtained in the step (1) to-22 ℃, slowly dripping 0.4mol of titanium tetrachloride solution into the homogeneous solution obtained in the step (1) by using a constant-pressure dripping pipe, stirring and reacting at-22 ℃ for 1 hour after dripping is finished, heating to 10 ℃ within 30 minutes, reacting at 10 ℃ for 1 hour, heating to 90 ℃ within 2 hours, and stirring and reacting at 90 ℃ for 2 hours to obtain a suspension of a catalyst component;
(3) Reducing the temperature of the suspension to 50 ℃, standing, settling, washing once with 80 ml of toluene, and washing three times with hexane, wherein the amount of hexane used in each time is 80 ml; after washing, the mixture is dried by blowing high-purity nitrogen at the bath temperature of 75 ℃ to obtain solid flowable powder. The catalyst was evaluated in the same manner as in example 1, and the polymerization results are shown in Table 1, and the results of the catalyst scanning electron microscope test are shown in FIG. 5.
Comparative example 4
(1) Weighing 0.037mol of magnesium dichloride, adding into a glass reaction kettle, adding 0.038mol of tetrabutyl titanate, adding 0.037mol of ethylene glycol monobutyl ether, 4.57mmol of tetrahydrofuran and 110 ml of toluene, heating to 60 ℃, stirring for 6 hours, and reacting until a transparent solution is formed;
(2) Cooling the solution in the step (1) to-22 ℃, slowly dripping 0.4mol of titanium tetrachloride solution into the homogeneous solution obtained in the step (2) by using a constant-pressure liquid dripping pipe, after finishing dripping, stirring and reacting at-22 ℃ for 1 hour, heating to 10 ℃ within 30 minutes, reacting at 10 ℃ for 1 hour, then heating to 90 ℃ within 2 hours, and stirring and reacting at 90 ℃ for 2 hours to obtain a suspension of the catalyst component;
(3) Cooling the suspension to 50 ℃, standing, settling, washing once with 80 ml of toluene, and washing three times with hexane, wherein the amount of hexane used in each time is 80 ml; after washing, the mixture is dried by blowing high-purity nitrogen at the bath temperature of 75 ℃ to obtain solid flowable powder.
The catalyst was evaluated in the same manner as in example 1, and the polymerization results are shown in Table 1 and the results of the scanning electron microscope test of the catalyst are shown in FIG. 6.
TABLE 1
(wherein: BD-bulk Density; SPAN-particle size distribution Width)
As can be seen from the experimental data of the examples and the comparative examples in Table 1, the catalyst obtained by the present invention has a narrow particle size distribution width and a high polymer bulk density while maintaining the activity at a high level. As can be seen from the comparison of FIGS. 1 to 6, the catalyst of the present invention has a particle type of a sphere-like shape, uniform particles and good dispersibility, as compared with the catalyst of the comparative example. The catalyst particles obtained in the comparative example were sticky and had irregular particle morphology.
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 (15)
1. A catalyst component for the polymerization of ethylene comprising the reaction product of: a magnesium compound, an oxygen-containing titanium compound, an organic epoxy compound, an alcohol ether compound, an ether compound and a halogenating agent;
wherein the magnesium compound is Mg (OR) with a general formula (I) 1 ) m Cl 2-m Shown by the formula, R 1 Is C 2 ~C 20 A saturated or unsaturated, linear or branched hydrocarbon radical, or is C 3 ~C 20 Saturated or unsaturated cyclic alkyl, m is more than or equal to 0 and less than or equal to 2; the oxygen-containing titanium compound is Ti (OR) with a general formula (II) 2 ) n Cl 4-n Shown by the formula, R 2 Is C 2 ~C 20 Saturated or unsaturated, straight-chain or branched-chain hydrocarbon radicalsOr is C 3 ~C 20 Saturated or unsaturated cyclic alkyl, n is more than 0 and less than or equal to 4; the organic epoxy compound is selected from at least one of oxides, glycidyl ethers and internal ethers of aliphatic olefins with 2 to 8 carbon atoms, dienes or halogenated aliphatic olefins or dienes; the alcohol ether compound is represented by the general formula (III) R 3 OR 4 OH is represented by R 3 、R 4 Identical or different, each independently is C 2 ~C 20 A saturated or unsaturated, linear or branched hydrocarbon radical, or C 3 ~C 20 A saturated or unsaturated cyclic hydrocarbon group; the ether compound is at least one selected from anisole, phenetole, propyl ether, butyl ether, isopropyl ether, isobutyl ether, 1, 4-dioxane, tetrahydrofuran, ethylene oxide, 1, 2-propylene oxide, 1, 2-butylene oxide, cis 2, 3-butylene oxide, trans 2, 3-butylene oxide, 9- (bismethoxymethyl) fluorene, isoamyl ether and amyl ether; the halogenating reagent is shown as a general formula (IV) R 5 a MX b M is a third, fourth or fifth main group element or a transition metal element, X is halogen, R is 5 Is C 2 ~C 20 Saturated or unsaturated, linear or branched hydrocarbon radical, C 3 ~C 20 Saturated or unsaturated cycloalkyl or alkoxy radicals, C 6 ~C 20 Aromatic groups, a =0, 1,2,b =1, 2,3, 4;
the dosage of the oxygen-containing titanium compound is 0.1 to 20 moles, the dosage of the organic epoxy compound is 0.1 to 10 moles, the dosage of the alcohol ether compound is 0.1 to 10 moles, the dosage of the ether compound is 0.01 to 10 moles, and the dosage of the halogenating agent is 0.5 to 50 moles per mole of magnesium in the magnesium compound.
2. Catalyst component for the polymerization of ethylene according to claim 1, characterized in that:
R 1 is C 2 ~C 10 Alkyl groups of (a); and/or the presence of a gas in the gas,
R 2 is C 2 ~C 10 Alkyl groups of (a); and/or the presence of a gas in the gas,
the organic epoxy compound is at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether and diglycidyl ether; and/or the presence of a gas in the gas,
R 3 or R 4 Is C 2 ~C 10 A saturated or unsaturated, linear or branched hydrocarbon radical, or is C 3 ~C 10 Saturated or unsaturated cyclic hydrocarbon groups.
3. Catalyst component for the polymerization of ethylene according to claim 2, characterized in that:
the magnesium compound is selected from alkoxy magnesium compound and/or magnesium chloride.
4. Catalyst component for the polymerization of ethylene according to claim 3, characterized in that:
the magnesium compound is at least one selected from diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, dioctoxymagnesium and magnesium dichloride.
5. Catalyst component for the polymerization of ethylene according to claim 2, characterized in that:
the oxygen-containing titanium compound is titanate.
6. Catalyst component for the polymerization of ethylene according to claim 5, characterized in that:
the oxygen-containing titanium compound is selected from at least one of tetrabutyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate and tetra-tert-butyl titanate.
7. Catalyst component for the polymerization of ethylene according to claim 2, characterized in that:
the alcohol ether compound is selected from an ethylene glycol ether compound or a propylene glycol ether compound.
8. Catalyst component for the polymerization of ethylene according to claim 7, characterized in that:
the alcohol ether compound is at least one selected from 1-butoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, 1-methoxy-2-propanol, ethylene glycol monohexyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether and ethylene glycol monobutyl ether.
9. Catalyst component for the polymerization of ethylene according to claim 2, characterized in that:
the halogenating agent is selected from TiCl 4 、R 6 n TiCl 4-n 、SiCl 4 、R 6 nSiCl 4-n 、R 6 n AlCl 4-n Wherein R is 6 Is C 2 ~C 20 Saturated or unsaturated, linear or branched hydrocarbon radical, C 3 ~C 20 Saturated or unsaturated cycloalkyl or alkoxy radicals, C 6 ~C 20 An aromatic radical, n is an integer of 0<n<4。
10. Catalyst component for the polymerization of ethylene according to claim 9, characterized in that:
the halogenating agent is at least one of dichloroethylaluminum, monochlorodiethylaluminum, dichloroisobutylaluminum, monochlorodiisobutylaluminum, dichloroisopropylaluminum, monochlorodiisopropylaluminum, silicon tetrachloride, titanium tetrabromide, titanium tetraiodide, monochlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium.
11. The catalyst component for ethylene polymerization according to any one of claims 1 to 10, characterized in that:
the dosage of the oxygen-containing titanium compound is 0.1 to 5.0 mol per mol of magnesium in the magnesium compound;
the dosage of the organic epoxy compound is 0.1 to 5.0 mol;
the dosage of the alcohol ether compound is 0.1 to 5.0 mol;
the amount of the ether compound is 0.05 to 5 mol;
the amount of the halogenating agent used is 0.5 to 20 mol.
12. A process for the preparation of a catalyst component for the polymerization of ethylene according to any one of claims 1 to 11, comprising the steps of:
(1) Contacting a magnesium compound, an oxygen-containing titanium compound, an organic epoxy compound and an alcohol ether compound, and reacting to form a transparent solution;
(2) Contacting the solution obtained in the step (1) with a halogenating reagent, and reacting to obtain a suspension;
(3) Curing the suspension obtained in the step (2), washing and drying to obtain the catalyst component;
wherein the ether compound is added in step (1), or added to the transparent solution obtained in step (1), or added in step (2), or added in step (3).
13. A catalyst for the polymerization of ethylene comprising the reaction product of:
(A) A catalyst component as claimed in any one of claims 1 to 11; or a catalyst component prepared by the preparation method according to claim 12;
(B) Is AlR of the general formula (IV) p X 3-p An organoaluminum compound represented by the formula (I), wherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, p is an integer of 1<p≤3。
14. The method for preparing a catalyst for ethylene polymerization according to claim 13, comprising the step of mixing and reacting the catalyst component and the organoaluminum compound.
15. Use of the catalyst of claim 13 in ethylene polymerization.
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| CN105085734A (en) * | 2014-04-29 | 2015-11-25 | 中国石油化工股份有限公司 | Preparation method for catalyst composition for alkene polymerization |
| CN107840910A (en) * | 2016-09-18 | 2018-03-27 | 中国石油化工股份有限公司 | Catalytic component for ethylene polymerization and preparation method thereof, catalyst and its application |
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| CN105085734A (en) * | 2014-04-29 | 2015-11-25 | 中国石油化工股份有限公司 | Preparation method for catalyst composition for alkene polymerization |
| CN107840910A (en) * | 2016-09-18 | 2018-03-27 | 中国石油化工股份有限公司 | Catalytic component for ethylene polymerization and preparation method thereof, catalyst and its application |
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