CN110041457B - Alpha-olefin polymerization catalyst, preparation method thereof and alpha-olefin polymerization method - Google Patents
Alpha-olefin polymerization catalyst, preparation method thereof and alpha-olefin polymerization method Download PDFInfo
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- CN110041457B CN110041457B CN201810036232.0A CN201810036232A CN110041457B CN 110041457 B CN110041457 B CN 110041457B CN 201810036232 A CN201810036232 A CN 201810036232A CN 110041457 B CN110041457 B CN 110041457B
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Abstract
The invention discloses a preparation method of an alpha-olefin polymerization catalyst, which comprises the following steps: s1 pretreatment of the carrier: carrying out alcoholization on the carrier in cyclohexane by using organic alcohol to obtain a carrier alcohol compound; s2 active component loading: diluting an active component titanium compound by 2-4 times with cyclohexane, and dropwise adding the diluted active component titanium compound into a carrier alcohol compound for stirring to obtain a main catalyst; s3 purification of the main catalyst: washing the catalyst semi-finished product by using cyclohexane to obtain slurry containing the catalyst semi-finished product, and drying in vacuum to obtain a purified main catalyst; s4 reduction of main catalyst: and (3) adopting a cocatalyst as a reducing agent, and reducing to obtain a catalyst finished product. A process for the polymerization of alpha-olefins. The invention also discloses a catalyst prepared by the method, and an alpha-olefin polymerization method using the catalyst prepared by the preparation method as a catalyst.
Description
Technical Field
The present invention relates to an alpha-olefin polymerization catalyst, a preparation method thereof, and a polymerization method of alpha-olefin catalyzed by the catalyst, and particularly to an alpha-olefin polymerization catalyst used as a synthetic lubricant base oil, a preparation method thereof, and a polymerization method of alpha-olefin catalyzed by the catalyst.
Background
The lubricating oil is oily liquid or semisolid which is coated on the surface of moving objects such as machine bearings and the like and can play roles of lubrication, cooling, cleaning, sealing, rust prevention, buffering and the like. The general lubricating oil consists of base oil and additives, wherein the base oil is the base of the lubricating oil, and the quality of the base oil has great influence on the performance of products. The base oil is classified into mineral lubricating oil, animal and vegetable oil and synthetic lubricating oil. At present, most of lubricating oil base oil is mainly mineral lubricating oil; the animal and vegetable oil has the disadvantages of easy oxidation and short service life although being environment-friendly and good in reproducibility; the synthetic lubricating oil is completely synthesized by an organic method, and is lubricating oil base oil with a certain chemical structure and special performance.
Synthetic lubricating oils can be classified into the following groups according to their chemical structures:
(1) synthetic hydrocarbon oils including polyalphaolefins, polyisobutylenes, alkylbenzenes, and the like;
(2) synthetic oil of organic acid esters;
(3) polyether type synthetic oil;
(4) a phosphate ester;
(5) a fluorine-containing oil;
(6) contains silicone oil.
Among them, poly-alpha-olefin is one of synthetic base oils. Polyalphaolefins (PAO) are made by polymerizing ethylene to produce alpha olefins, which are further polymerized and hydrogenated. It is a relatively common synthetic lubricating oil base oil, and has the widest application range.
Polyalphaolefin base oils have a slightly skewed temperature-viscosity profile, a lower pour point, excellent engine performance and advantages as engine oils. As a synthetic oil, there are very excellent characteristics, firstly, high thermal oxidation stability (thermal stability means that a good viscosity index can be maintained in a wide temperature range, so that an engine can be started easily and safely in cold weather, and at the same time, the engine can be protected to the maximum under high speed and heavy load) because of the particularity of the molecular structure of the synthetic oil, so that the synthetic oil can have higher flow and penetration (compared with mineral oil). Its chemical stability means that the synthetic oil does not undergo any chemical changes (oxidation, waxing, etc.) that impair its performance during operation in the engine, that is to say the travel incrustation and the lacquer (meaning a transparent, strong, non-melting film of oxides that forms on surfaces at very high temperatures) are very small, which means that synthetic oils have the advantage of being 3 times or more higher than mineral oils, have pour points that are much lower than mineral oils (-50 ℃, minus 60 ℃), and have a very high viscosity index, that is to say the viscosity does not change much with changes in temperature, which makes it possible to start the engine easily in cold weather. Secondly, the viscosity index remains high above 100 ℃ and therefore the oil film separating the friction surfaces does not destroy the optimal thermal state, enabling to reduce the mechanical losses of the engine as a whole and to reduce the wear of the parts. These oils possess all the advantages of mineral oils at the same time. The lubricating oil is easy to flow, can reduce power loss caused by friction, can reduce oil consumption, and has low oil passing temperature, namely, the engine can be allowed to normally work at minus 40 ℃. These oils are relatively low in volatility at high temperatures, which increases the useful life of the oil beyond 3 kilometers.
Therefore, the poly-alpha-olefin synthetic oil (PAO for short) has good viscosity-temperature performance and low-temperature fluidity, and is ideal base oil for preparing high-grade and special lubricating oil.
In the face of the rapid development of the mechanical industry of various countries in the world, the requirements of people on the quality of lubricating oil are continuously improved. The high-quality PAO (poly-alpha-olefin) synthetic lubricating oil mainly depends on the current situation of high-price import and the like, and the development of high-performance lubricating oil has practical significance.
The catalyst system of the prior foreign PAO synthesis process technology is divided into a homogeneous phase method and a heterogeneous phase method, wherein the homogeneous phase method comprises the following steps: cp of BP2ZrCl2MAO metallocene catalyst, Et from Uniroyal3Al/TiCl4/RCl Ziegler catalyst, Chevron's BF3i-BuOH/EtOH and AlCl3Trimethylamine hydrochloride ionic liquid catalyst and Neste BF3AlCl of/n-BuOH cationic catalyst, Indian Oil3/Ti(OBu)4Cationic catalysts, and the like; heterogeneous methods include: exxon Mobil Cr/MCM-41 molecular sieve catalyst and WOX/ZrO2Bimetallic oxides, and the like. Unide chemical Co Ltd in TiCl4With Et3Al2Br3The formed catalytic system catalyzes 1-decene to polymerize, the molecular weight of the polymerization product is 500-5000-2And the viscosity index reaches 170. Mobil oil company loads chromium acetate on a specific surface area of 300m2The roasting temperature of 8-12 meshes of silicon oxide per gram is 800 ℃, CO reduction is carried out at 300 ℃, the catalyst prepared under the condition is used for carrying out 1-hexene polymerization test, the viscosity of the obtained product at 100 ℃ is 151, the viscosity index is 164, and the viscosity of the product at 100 ℃ is 157.6 and the viscosity index is 217 when the polymerization test is carried out by taking 1-decene as a raw material. SpectraSyn Elite introduced by Exxon Mobil in 2010TMCompared with the traditional PAO, the metallocene PAO product has the characteristics of good shear stability and viscosityHigh degree index (PAO150 viscosity index over 200), designed by Mobil corporation (Cp)*)MX1X2The non-bridged chain double-metallocene single metal catalyst can realize the control of the degree of reaction polymerization by adjusting the substituent on the metallocene ring, and can produce PAO with different viscosities. Adopted by Nippon Kogyo Co Ltd (Cp)1)R1R2(Cp2)M X1X2The ultra-high viscosity index PAO is prepared by catalyzing a mixture of octene-1, decene-1 and dodecene-1 by using a double-bridge chain double-metallocene single metal catalyst, the viscosity index of the PAO can reach 215, and the kinematic viscosity of the PAO at 100 ℃ is 296mm2The pour point was-30 ℃.
Related scientific research work is also carried out in the field of PAO base oil at home, and TiCl is used by Beijing university of chemical industry4With Et21-decene polymerization research is carried out on AlCl, the polymerization activity reaches 198.6kg of PAO/mol Ti, the content of tripolymer is 45%, the content of tetramer is 31%, the polymerization product exists in a head-tail polymerization mode, and the product performance is excellent. Rac-Et (1-Ind) at the university of eastern China2ZrCl2MAO single-bridge chain double-metallocene single-metal catalytic system with Zr/decene-1 molar ratio of 8X 10-5The conversion of decene-1 was 91.62% at 50 ℃ for 60 min. The overall performance of the polymerization product is excellent, and the kinematic viscosity at 100 ℃ is 393.93mm2And/s, viscosity index 271. Northeast university of Petroleum adopted (Cp) MX1X2The single bridge chain single metallocene catalyst takes a boron compound as a cocatalyst, catalyzes decene-1 to prepare PAO, and the Viscosity Index (VI) of the prepared PAO with the ultrahigh viscosity index can reach 238 at the temperature of 60 ℃. In 2011, the ionic liquid system is used as a catalyst by China petrochemical engineering science and research institute to prepare the product with the kinematic viscosity of more than 40mm at 100 DEG C2Excellent PAO product per second.
Among them, Ziegler-Natta catalysts have been known for about 60 years, and although polyolefin catalysts such as metallocene and non-metallocene have appeared in the period, the problems of industrialization are more, for example, the cocatalyst is expensive, and the loading of the main catalyst is difficult. Therefore, in view of the current industrial production and market share, the traditional Z-N catalyst will be the leading one in the field of olefin polymerization for some time in the future.
Patent 96106647.4X discloses an olefin polymerization catalyst and its preparation method, which comprises the step of supporting MgCl2Dissolved in a mixture of an alcohol and an alkane to form liquid MgCl2Alcohol adducts, such liquid MgCl2Alcohol adducts with TiCl4The olefin polymerization catalyst is obtained by contact, but the hydrogen regulation performance of the catalyst is poor, and the melt index MFR of the polyethylene can only be adjusted within 0.1g/10 min-220 g/10 min.
Patent 200480008242.X discloses an olefin polymerization catalyst and its preparation method, MgCl is used as carrier2Preparation of solid MgCl by direct dissolution in ethanol2Alcohol adduct and further reacting TiCl4Supported on solid MgCl2The alcohol adduct gives the olefin polymerization catalyst.
Patent 201110382706.5 discloses an olefin polymerization catalyst and its preparation method, which comprises the step of supporting MgCl2Solid MgCl is prepared by dissolving in organic solvent of isooctyl alcohol and ethanol2Alcohol-synthesizing, then adding TiCl4Supported on solid MgCl2The olefin polymerization catalyst is obtained on the alcohol compound, and the catalyst has good hydrogen adjusting effect. But the catalyst activity is low and the main catalyst particles are easily adhered to the wall of the container.
Patents CN85100997A, CN200810227369.0, CN200810227371.8 and CN200810223088.8 disclose an olefin polymerization catalyst and a preparation method thereof, wherein MgCl is prepared2The particles are dissolved in a system of an organic epoxy compound, an organic phosphorus compound and an inert organic solvent to obtain MgCl2Solution, and TiCl4And (3) contacting to prepare the main catalyst for olefin polymerization. The organophosphorus compound is used to react MgCl2A necessary component of the solvent system in which the particles are dissolved.
Patent 2013105985560 discloses adding an inert organic solvent, a monohydric alcohol having less than 5 carbon atoms, an alcohol having more than 5 carbon atoms, and MgCl during the catalyst preparation process2After the particles are dissolved, an organic phosphorus compound, an organosilicon compound and an organic boron compound are added to prepare liquid MgCl2Alcohol-synthesizing, then adding TiCl4With such liquidsBulk MgCl2The alcohol compound is contacted, and then the polyhydroxy solid is added to obtain the olefin polymerization catalyst, which can improve the particle shape of the solid main catalyst, the hydrogen regulation performance of the catalyst for catalyzing olefin polymerization, and the bulk density of polyolefin.
Patent 201310034134 discloses adding an inert organic solvent, an alcohol having less than 5 carbon atoms, an alcohol having more than 5 carbon atoms, MgCl during the catalyst preparation process2After the particles are dissolved, the organic phosphorus compound and the organic silicon compound are added to prepare liquid MgCl2Alcohol-synthesizing, then adding TiCl4With such liquid MgCl2The alcohol compound is contacted, and then the polyhydroxy solid is added to obtain the olefin high-efficiency polymerization catalyst, which can improve the particle form of the solid main catalyst and the hydrogen regulation performance of the catalyst for catalyzing olefin polymerization.
Patent 201210436136.8 discloses adding an inert organic solvent, an alcohol having less than 5 carbon atoms, an alcohol having more than 5 carbon atoms, MgCl during the catalyst preparation process2After the particles are dissolved, the organic phosphorus compound and the organic silicon compound are added to prepare liquid MgCl2Alcohol-synthesizing, then adding TiCl4With such liquid MgCl2The alcohol compound is contacted to obtain the olefin high-efficiency polymerization catalyst, which can improve the particle form of the solid main catalyst and the hydrogen regulation performance of the catalyst for catalyzing olefin polymerization; the patent finds that after the magnesium halide carrier is dissolved, the organophosphorus compound is added, so that the catalytic activity of the catalyst can be obviously improved, the static electricity of solid main catalyst particles can be eliminated, and the main catalyst particles are not adhered to the wall of a container.
Patent CN106519084A provides a preparation method of an olefin polymerization catalyst, which comprises the following steps: 1) dispersing a magnesium compound carrier in an inert organic solvent, adding alcohol with the carbon number of 2-15, and stirring and dissolving for 1-5 h at 90-150 ℃; 2) cooling the solution of 1) to 30-80 ℃, adding a star-shaped organic aza ether compound, and reacting for 0.5-3 h; 3) contacting the system obtained in the step 2) with transition metal halide at the temperature of between 25 ℃ below zero and 30 ℃, reacting for 0.5 to 5 hours at the temperature of between 25 ℃ below zero and 30 ℃, heating the system to 50 ℃ to 120 ℃, reacting for 0.5 to 5 hours, gradually separating out solid particles in the heating process, washing the product for 4 to 6 times by using toluene or n-hexane after the reaction is finished, and filtering to remove unreacted substances; vacuum drying to obtain the powdered solid main catalyst. The vacuum drying temperature is 40 ℃ to 90 ℃; the vacuum drying time is 0.5 to 5 hours, preferably 1 to 4 hours.
Common similar Ziegler Natta catalysts mostly adopt an aluminum alkyl as a cocatalyst, and the reduction degree of an active center is difficult to control well, for example, only triethyl aluminum is used as the cocatalyst, the viscosity index of a product can be ensured, but the polymerization activity is reduced; the diethyl aluminum monochloride is used as a cocatalyst, so that the polymerization activity is high, and the viscosity and the performance of the product are reduced.
Disclosure of Invention
In order to solve the problems, the invention adopts the composite alkyl aluminum as the cocatalyst, thereby not only ensuring the polymerization activity, but also synthesizing the high-performance PAO product.
To this end, the present invention provides a method for preparing an α -olefin polymerization catalyst, comprising the steps of:
s1 pretreatment of the carrier: carrying out alcoholization on the carrier in cyclohexane by using organic alcohol to obtain a carrier alcohol compound;
s2 active component loading: diluting an active component titanium compound by 2-4 times with cyclohexane, and dropwise adding the diluted active component titanium compound into a carrier alcohol compound for stirring to obtain a main catalyst;
s3 purification of the main catalyst: washing the catalyst semi-finished product by using cyclohexane to obtain slurry containing the catalyst semi-finished product, and drying in vacuum to obtain a purified main catalyst;
s4 reduction of main catalyst: adopting a cocatalyst as a reducing agent, and reducing to obtain a catalyst finished product;
the cocatalyst is selected from two of trimethylaluminum, triethylaluminum, diethyl aluminum monochloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, methylaluminoxane and ethylaluminoxane, and the molar ratio of the two components is 1: 0.1-10.
The preparation method of the alpha-olefin polymerization catalyst provided by the invention is characterized in that the molar ratio of two components in the cocatalyst is preferably 1: 0.1-2; more preferably 1:0.1 to 0.5.
The preparation method of the alpha-olefin polymerization catalyst is characterized in that the cocatalyst is preferably diethyl aluminum monochloride and triethyl aluminum, and the molar ratio of the diethyl aluminum monochloride to the triethyl aluminum is preferably 1: 0.1-1; the molar ratio of the two is more preferably 1:0.2 to 0.5.
In the preparation method of the α -olefin polymerization catalyst according to the present invention, in step S2, the amount of the active component is preferably 0.1% to 10% by weight of the carrier alcohol hydrate.
In the preparation method of the alpha-olefin polymerization catalyst, in step S4, the molar ratio of the main catalyst to the co-catalyst component is preferably 1: 0.1-10 in terms of active component.
In the preparation method of the alpha-olefin polymerization catalyst, in step S4, the molar ratio of the main catalyst to the cocatalyst component is preferably 1:1 to 20 in terms of the active component.
The preparation method of the alpha-olefin polymerization catalyst, provided by the invention, comprises the following steps of pretreatment of the carrier: heating the carrier at 200 ℃ for 24 hours in the protection of nitrogen; preparing a suspension of a carrier and cyclohexane in a molar ratio of 1:20, and dropwise adding a suspension of a carrier and cyclohexane in a molar ratio of 1: 1-10 of n-butanol, and reacting the mixture with a carrier to generate an alcohol compound.
The preparation method of the alpha-olefin polymerization catalyst, provided by the invention, comprises the following steps of: diluting the active component with cyclohexane 2-4 times at 10-100 deg.C, adding carrier alcohol, and stirring for 1-4 hr.
The preparation method of the alpha-olefin polymerization catalyst, provided by the invention, is characterized in that the catalyst purification step is preferably as follows: performing multiple times of hot washing by using cyclohexane, and transferring out a washing supernatant to obtain supported catalyst slurry; and vacuum drying to obtain the purified supported catalyst.
In the method for preparing an α -olefin polymerization catalyst according to the present invention, the titanium compound is preferably at least one selected from titanium tetrachloride, titanium trichloride and titanium isopropoxide.
In the method for preparing an α -olefin polymerization catalyst according to the present invention, the carrier is preferably at least one selected from the group consisting of silica gel, alumina, magnesium chloride and MCM-41.
The invention also provides an alpha-olefin polymerization catalyst which is prepared by the preparation method and comprises a main catalyst and a cocatalyst, wherein the main catalyst consists of a carrier and an active component, the active center is a titanium compound, the carrier can be one of silica gel, aluminum oxide, magnesium chloride and MCM-41, the cocatalyst is two of trimethylaluminum, triethylaluminum, diethyl aluminum monochloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, methylaluminoxane and ethylaluminoxane, and the molar ratio of the two components is 1: 0.1-10.
The invention also provides a polymerization method of alpha-olefin, which takes the catalyst prepared by the preparation method as a catalyst to catalyze linear or nonlinear alpha-olefin to polymerize and prepare the lubricating oil base oil, and the polar or nonpolar solvent used in the polymerization reaction process is alkane, arene or ionic liquid.
The method for polymerizing alpha-olefin according to the present invention, wherein the linear or non-linear alpha-olefin is preferably at least one selected from the group consisting of 1-hexene, 1-octene and 1-decene.
The polymerization method of alpha-olefin according to the present invention is preferably such that the reaction conditions for the polymerization are: the temperature is 20-180 ℃, the pressure is 0.1-5MPa, and the time is 1-10 h.
The alpha-olefin polymerization catalyst is prepared by the following method:
a three-neck reaction flask equipped with a stirrer and a thermometer was purged with high-purity nitrogen 3 times, and MgCl was added to the reaction vessel2With cyclohexane; at 25-100 ℃, dropwise adding n-butanol at a slow speed to generate an alcohol compound with the carrier;
after the reaction is finished, reducing the temperature, diluting the active component by 2-4 times with cyclohexane at 10-100 ℃ to obtain titanium tetrachloride diluent, adding a carrier alcohol compound, and stirring for 0.5-3 h;
after the reaction of the titanium-loaded active center is finished, the reaction solution is filtered under the protection of inert gas, and the generated titanium-loaded active center is treatedCarrying out multiple times of hot washing on the solid material by using cyclohexane, and transferring out a washing supernatant to obtain carrier catalyst slurry; drying in vacuum to obtain MgCl2Loaded with TiCl4A catalyst.
The polymerization method of alpha-olefin adopts a slurry polymerization reaction method, and comprises the following specific steps:
replacing the glass three-neck bottle with high-purity nitrogen for several times, adding a certain amount of cyclohexane solvent into the reactor under the protection of nitrogen, and adding metered MgCl2Loaded with TiCl4The catalyst is stirred for a certain time at room temperature, and then the cocatalyst is added at a slow speed. After the cocatalyst is added, stirring for a certain time, adding alpha-olefin into the reactor, adjusting to the reaction temperature, and reacting for a certain time. And filtering, alkali washing, water washing and reduced pressure distillation are carried out on the product to separate unreacted monomers and generated dimer, so as to obtain the PAO product.
Compared with the prior art, the invention has the following characteristics: the supported titanium catalyst is used as a main catalyst, two kinds of alkyl aluminum are used as auxiliary catalysts together, the reduction capability of different auxiliary catalysts to the metal active center of the main catalyst is different, the control of the valence of the metal active center of the main catalyst is realized by selecting proper auxiliary catalyst types and proportions, the polymerization activity of the catalyst and the polymerization degree of a product are controlled, and then the poly alpha-olefin base oil with the required viscosity is synthesized by adjusting the composition of the catalyst formula.
Compared with the common catalyst for synthesizing the poly-alpha-olefin oil, the catalyst is used for catalyzing linear or nonlinear alpha-olefin polymerization, the viscosity index of the base oil can be obviously improved, and the poly-alpha-olefin base oil with different target viscosities can be synthesized by adjusting the formula composition of the catalyst.
The preparation method of the alpha-olefin polymerization catalyst provided by the invention is simple and low in cost, and the catalyst prepared by the method has the characteristics of high catalytic activity, easiness in separation of the catalyst and a product, no environmental pollution and the like.
Drawings
FIG. 1 is a process flow diagram of a process for preparing an alpha-olefin polymerization catalyst according to the present invention.
Detailed Description
The following examples are intended to further illustrate the process of the present invention but should not be construed as limiting thereof.
The polymer related data in the examples were obtained according to the following test methods:
(1) viscosity: according to GB/T265-1988 petroleum product kinematic viscometry and dynamic viscometer algorithms.
(2) Viscosity index: according to GB/T265-1988 petroleum product kinematic viscometry and dynamic viscometer algorithms.
Preparation example 1
Preparation of the procatalyst 1
A three-necked reaction flask equipped with a stirrer and a thermometer was purged with high-purity nitrogen 3 times, and 15.5g of MgCl was charged into the reaction vessel2With 50ml of cyclohexane; dripping 10ml of n-butanol at the speed of 3-4 seconds per drop at the temperature of 60 ℃ to enable the n-butanol and the carrier to generate an alcohol compound;
after the reaction is finished, reducing the temperature to 25 ℃, taking 2.55ml of titanium tetrachloride, adding cyclohexane with the volume ratio being twice that of the titanium tetrachloride to prepare a titanium tetrachloride solution, adding the titanium tetrachloride solution into the carrier alcohol complex at the speed of 3-4 seconds per drop while stirring, and continuously stirring for 1 hour after the dropping is finished;
after the reaction of the titanium-loaded active center is finished, filtering out reaction liquid under the protection of inert gas, carrying out multiple times of hot washing on the generated material by using cyclohexane, and transferring out washing supernatant to obtain high-efficiency carrier catalyst slurry; drying in vacuum to obtain MgCl2Loaded with TiCl4A catalyst.
Preparation example 2
Preparation of procatalyst 2
A three-necked reaction flask equipped with a stirrer and a thermometer was purged with high-purity nitrogen 3 times, and 15.5g of MgCl was charged into the reaction vessel2With 50ml of cyclohexane; dripping 10ml of n-butanol at the speed of 3-4 seconds per drop at the temperature of 60 ℃ to enable the n-butanol and the carrier to generate an alcohol compound;
after the reaction is finished, reducing the temperature to 25 ℃, taking 3.83ml of titanium tetrachloride, adding cyclohexane with the volume ratio being twice that of the titanium tetrachloride to prepare a titanium tetrachloride solution, adding the titanium tetrachloride solution into the carrier alcohol complex at the speed of 3-4 seconds per drop while stirring, and continuously stirring for 1 hour after the dropping is finished;
after the reaction of the titanium-loaded active center is finished, filtering out reaction liquid under the protection of inert gas, carrying out multiple times of hot washing on the generated material by using cyclohexane, and transferring out washing supernatant to obtain high-efficiency carrier catalyst slurry; drying in vacuum to obtain MgCl2Loaded with TiCl4A catalyst.
Preparation example 3
Preparation of the procatalyst 3
A three-necked reaction flask equipped with a stirrer and a thermometer was purged with high-purity nitrogen 3 times, and 15.5g of MgCl was charged into the reaction vessel2With 50ml of cyclohexane; dripping 10ml of n-butanol at the speed of 3-4 seconds per drop at the temperature of 60 ℃ to enable the n-butanol and the carrier to generate an alcohol compound;
after the reaction is finished, reducing the temperature to 25 ℃, taking 5.1ml of titanium tetrachloride, adding cyclohexane with the volume ratio being twice that of the titanium tetrachloride to prepare a titanium tetrachloride solution, adding the titanium tetrachloride solution into the carrier alcohol complex at the speed of 3-4 seconds per drop while stirring, and continuously stirring for 1 hour after the dropping is finished;
after the reaction of the titanium-loaded active center is finished, filtering out reaction liquid under the protection of inert gas, carrying out multiple times of hot washing on the generated material by using cyclohexane, and transferring out washing supernatant to obtain high-efficiency carrier catalyst slurry; drying in vacuum to obtain MgCl2Loaded with TiCl4A catalyst.
Comparative example 1
Olefin polymerization with procatalyst 1
The slurry polymerization method was used for this experiment. The glass three-necked flask was purged with high-purity nitrogen 3 times, 20ml of cyclohexane solvent was added to the reactor under nitrogen protection, and 3.11g of MgCl prepared in example 1 was added2Loaded with TiCl4And (3) stirring the catalyst at room temperature for 5min, and adding 1.14ml of diethyl aluminum monochloride (DEAC) at a speed of 3-4 s/drop to reduce the main catalyst.
And after the addition of the cocatalyst is finished, stirring for 30min, then adding 120ml of alpha-decene into the reactor, adjusting the reaction temperature to 80 ℃, and reacting for 4 h. The product was filtered, washed with alkali, washed with water, and distilled under reduced pressure to separate unreacted monomer and dimer produced, yielding 46.22g of PAO product. The results of the product analysis are shown in Table 1.
Example 1
Olefin polymerization with procatalyst 1
The glass three-necked flask was purged with high-purity nitrogen 3 times, 20ml of cyclohexane solvent was added to the reactor under nitrogen protection, and 3.11g of MgCl prepared in example 1 was added2Loaded with TiCl4After stirring the catalyst at room temperature for 5min, 1.14ml of diethyl aluminum monochloride (DEAC) and 0.25ml of triethyl aluminum (TEA) were added thereto at a rate of 3 to 4 sec/drop to reduce the supported catalyst.
And after the addition of the cocatalyst is finished, stirring for 30min, then adding 120ml of alpha-decene into the reactor, adjusting the reaction temperature to 80 ℃, and reacting for 4 h. The product was filtered, washed with alkali, washed with water, and distilled under reduced pressure to separate unreacted monomer and dimer produced, yielding 25.1g of PAO product. The results of the product analysis are shown in Table 1.
Example 2
Olefin polymerization with procatalyst 1
The glass three-necked flask was purged with high-purity nitrogen 3 times, 20ml of cyclohexane solvent was added to the reactor under nitrogen protection, and 3.11g of MgCl prepared in example 1 was added2Loaded with TiCl4And (3) stirring the catalyst at room temperature for 5min, and then adding 1.14ml of diethyl aluminum chloride and 0.37ml of triethyl aluminum at the speed of 3-4 s/drop to reduce the supported catalyst.
And after the addition of the cocatalyst is finished, stirring for 30min, then adding 120ml of alpha-decene into the reactor, adjusting the reaction temperature to 80 ℃, and reacting for 4 h. The product was filtered, washed with alkali, washed with water, and distilled under reduced pressure to separate unreacted monomer and dimer produced, yielding 35.1g of PAO product. The results of the product analysis are shown in Table 1.
Example 3
Olefin polymerization with procatalyst 1
The glass three-necked flask was replaced with high-purity nitrogen gas 3 times, 20ml of cyclohexane solvent was added to the reactor under nitrogen protection, and 3.11g of Mg prepared in example 1 was addedCl2Loaded with TiCl4And (3) stirring the catalyst at room temperature for 5min, and then adding 1.14ml of diethyl aluminum chloride and 0.50ml of triethyl aluminum at the speed of 3-4 s/drop to reduce the supported catalyst.
And after the addition of the cocatalyst is finished, stirring for 30min, then adding 120ml of alpha-decene into the reactor, adjusting the reaction temperature to 80 ℃, and reacting for 4 h. The product was filtered, washed with alkali, washed with water, and distilled under reduced pressure to separate unreacted monomer and dimer produced, yielding 34.3g of PAO product. The results of the product analysis are shown in Table 1.
Example 4
Olefin polymerization with procatalyst 1
The glass three-necked flask was purged with high-purity nitrogen 3 times, 20ml of cyclohexane solvent was added to the reactor under nitrogen protection, and 3.11g of MgCl prepared in example 1 was added2Loaded with TiCl4After stirring the catalyst at room temperature for 5 minutes, 1.14ml of diethylaluminum monochloride and 0.62ml of triethylaluminum were added at a rate of 3 to 4 seconds per drop.
And after the addition of the cocatalyst is finished, stirring for 30min, then adding 120ml of alpha-decene into the reactor, adjusting the reaction temperature to 80 ℃, and reacting for 4 h. The product was filtered, washed with alkali, washed with water, and distilled under reduced pressure to separate unreacted monomer and dimer produced, yielding 35.7g of PAO product. The results of the product analysis are shown in Table 1.
Comparative example 2
Olefin polymerization with procatalyst 1
The glass three-necked flask was purged with high-purity nitrogen 3 times, 20ml of cyclohexane solvent was added to the reactor under nitrogen protection, and 3.11g of MgCl prepared in example 1 was added2Loaded with TiCl4And (3) stirring the catalyst at room temperature for 5min, and adding 0.50ml of triethyl aluminum at the speed of 3-4 seconds per drop.
And after the addition of the cocatalyst is finished, stirring for 30min, then adding 120ml of alpha-decene into the reactor, adjusting the reaction temperature to 80 ℃, and reacting for 4 h. The product was filtered, washed with alkali, washed with water, and distilled under reduced pressure to separate unreacted monomer and dimer produced, yielding 15.6g of PAO product. The results of the product analysis are shown in Table 1.
Example 5
Olefin polymerization with procatalyst 2
The glass three-necked flask was purged with high-purity nitrogen 3 times, 20ml of cyclohexane solvent was added to the reactor under nitrogen protection, and 3.11g of MgCl prepared in example 2 was added2Loaded with TiCl4After stirring the catalyst at room temperature for 5min, 1.14ml of diethyl aluminum chloride and 0.50ml of triethyl aluminum were added thereto at a rate of 3 to 4 sec/drop.
And after the addition of the cocatalyst is finished, stirring for 30min, then adding 120ml of alpha-decene into the reactor, adjusting the reaction temperature to 80 ℃, and reacting for 4 h. The product was filtered, washed with alkali, washed with water, and distilled under reduced pressure to separate unreacted monomer and dimer produced, yielding 39.6g of PAO product. The results of the product analysis are shown in Table 2.
Example 6
Olefin polymerization with procatalyst 3
The glass three-necked flask was purged with high-purity nitrogen 3 times, 20ml of cyclohexane solvent was added to the reactor under nitrogen protection, and 3.11g of MgCl prepared in example 3 was added2Loaded with TiCl4After stirring the catalyst at room temperature for 5min, 1.14ml of diethyl aluminum chloride and 0.50ml of triethyl aluminum were added thereto at a rate of 3 to 4 sec/drop.
And after the addition of the cocatalyst is finished, stirring for 30min, then adding 120ml of alpha-decene into the reactor, adjusting the reaction temperature to 80 ℃, and reacting for 4 h. The product was filtered, washed with alkali, washed with water, and distilled under reduced pressure to separate unreacted monomer and dimer produced, yielding 53.8g of PAO product. The results of the product analysis are shown in Table 2.
TABLE 1 test results for decene oligomerization to PAO
As can be seen from Table 1, in comparative example 1, only diethylaluminum monochloride is used as a cocatalyst, the polymerization activity is high (e.g. the yield is high), and the viscosity of the product is reduced; comparative example 2 using only triethylaluminum as a cocatalyst, the viscosity index of the product could be secured, but the polymerization activity would be decreased. Examples 1-4 use a certain ratio of diethyl aluminum monochloride to triethyl aluminum as co-catalyst while obtaining better PAO product performance and polymerization activity. In particular, in example 2, when the ratio of diethyl aluminum monochloride to triethyl aluminum is 1:0.3, the maximum polymerization activity is achieved on the premise that the PAO product performance meets the standard.
TABLE 2 catalytic PAO Synthesis test results using catalysts with different preparation conditions
As can be seen from Table 2, the PAO yield increases significantly and the viscosity of the PAO product decreases slightly as the loading of Ti active sites on the procatalyst increases. Therefore, when the Ti active center loading on the main catalyst is 9.75 wt%, the optimal PAO product performance and polymerization activity can be obtained at the same time.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (14)
1. A method for preparing an α -olefin polymerization catalyst, the α -olefin being at least one selected from the group consisting of 1-hexene, 1-octene and 1-decene, comprising the steps of:
s1 pretreatment of the carrier: carrying out alcoholization on the carrier in cyclohexane by using organic alcohol to obtain a carrier alcohol compound; the process is as follows: heating the carrier at 200 ℃ for 24 hours in the protection of nitrogen; preparing a suspension of a carrier and cyclohexane in a molar ratio of 1:20, and dropwise adding a suspension of a carrier and cyclohexane in a molar ratio of 1: 1-10 of n-butanol, and reacting the n-butanol with a carrier to generate an alcohol compound;
s2 active component loading: diluting an active component titanium compound by 2-4 times with cyclohexane, and dropwise adding the diluted active component titanium compound into a carrier alcohol compound for stirring to obtain a main catalyst;
s3 purification of the main catalyst: washing the catalyst semi-finished product by using cyclohexane to obtain slurry containing the catalyst semi-finished product, and drying in vacuum to obtain a purified main catalyst;
s4 reduction of main catalyst: adopting a cocatalyst as a reducing agent, and reducing to obtain a catalyst finished product;
the cocatalyst is triethyl aluminum and diethyl aluminum monochloride, and the molar ratio of the two components is 1: 0.1-10.
2. The method for preparing an α -olefin polymerization catalyst according to claim 1, wherein the molar ratio of the two components in the co-catalyst is 1:0.1 to 2.
3. The method of preparing an α -olefin polymerization catalyst according to claim 1, wherein the co-catalyst is diethyl aluminum monochloride and triethyl aluminum in a molar ratio of 1:0.1 to 1.
4. The method for preparing an α -olefin polymerization catalyst according to claim 1, wherein the active component is used in an amount of 0.1 to 10% by weight of the carrier alcoholate in step S2.
5. The method for preparing an α -olefin polymerization catalyst according to claim 1, wherein in step S4, the molar ratio of the main catalyst to the co-catalyst component is 1:0.1 to 10.
6. The method for preparing an α -olefin polymerization catalyst according to claim 1, wherein in step S4, the molar ratio of the main catalyst to the co-catalyst component is 1:1 to 20.
7. The method for preparing an α -olefin polymerization catalyst according to claim 1, wherein the step of supporting the active component comprises: diluting the active component with cyclohexane 2-4 times at 10-100 deg.C, adding into the carrier alcoholic compound, and stirring for 1-4 hr.
8. The method for preparing an α -olefin polymerization catalyst according to claim 1, wherein the catalyst purification step is: performing multiple times of hot washing by using cyclohexane, and transferring out a washing supernatant to obtain supported catalyst slurry; and vacuum drying to obtain the purified supported catalyst.
9. The method for preparing an α -olefin polymerization catalyst according to claim 1, wherein the titanium compound is at least one selected from the group consisting of titanium tetrachloride, titanium trichloride and titanium isopropoxide.
10. The method of preparing an α -olefin polymerization catalyst according to claim 1, wherein the carrier is at least one selected from the group consisting of silica gel, alumina, magnesium chloride and MCM-41.
11. An alpha-olefin polymerization catalyst prepared by the preparation method of any one of claims 1 to 10, which is characterized by comprising a main catalyst and a cocatalyst, wherein the main catalyst consists of a carrier and an active component, the active center is a titanium compound, the carrier can be selected from one of silica gel, aluminum oxide, magnesium chloride and MCM-41, the cocatalyst is triethyl aluminum and diethyl aluminum chloride, and the molar ratio of the two components in the cocatalyst is 1: 0.1-10.
12. A method for polymerizing alpha-olefin, characterized in that the catalyst prepared by the preparation method of claim 1 is used as a catalyst to catalyze linear or non-linear alpha-olefin to polymerize and prepare lubricant base oil, and the polar or non-polar solvent used in the polymerization reaction process is alkane, aromatic hydrocarbon or ionic liquid.
13. The method of claim 12 wherein the linear or non-linear alpha olefin is selected from at least one of 1-hexene, 1-octene, and 1-decene.
14. The process for the polymerization of α -olefins according to claim 12, characterized in that said polymerization is carried out under the reaction conditions: the temperature is 20-180 ℃, the pressure is 0.1-5MPa, and the time is 1-10 h.
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| US3795616A (en) * | 1971-06-14 | 1974-03-05 | Gulf Research Development Co | Shear stable,multiviscosity grade lubricating oils |
| US4510342A (en) * | 1982-12-29 | 1985-04-09 | The Standard Oil Company | High viscosity index synthetic oils and synthesis thereof |
| JPS63308007A (en) * | 1987-06-09 | 1988-12-15 | Japan Synthetic Rubber Co Ltd | Production of liquid alpha-olefin polymer |
| CN101516921A (en) * | 2006-09-25 | 2009-08-26 | 巴塞尔聚烯烃意大利有限责任公司 | Magnesium methoxide based catalyst precursors and catalyst components obtained therefrom |
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