CN104356264A - Olefin polymerization catalyst as well as preparation method and application thereof - Google Patents
Olefin polymerization catalyst as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an olefin polymerization catalyst as well as a preparation method and application thereof. The olefin polymerization catalyst consists of a main catalyst component and a cocatalyst, wherein the main catalyst component is prepared by the following method: (1) reacting an organic magnesium compound with a hydroxyl group-containing compound in a carrier dispersant, adding a compound containing lone pair electrons for sufficient reaction, and then adding a titanium-containing compound and an inert carrier to obtain a suspension a; (2) reacting the organic magnesium compound with the hydroxyl group-containing compound in the carrier dispersant, adding the compound containing lone pair electrons for sufficient reaction, and then adding a vanadium-containing compound and the inert carrier to obtain a suspension b; (3) mixing the suspension a and the suspension b, adding an active center valence state regulator, and then drying through distillation to obtain the main catalyst component; the cocatalyst is at least one organic aluminum compound with the general formula of AlR5xCl3-x. Compared with the prior art, the olefin polymerization catalyst has the advantages of steady reaction efficiency within a relatively wide reaction temperature range, and the like.
Description
Technical field
The present invention relates to a kind of catalyzer, especially a kind of preparation method of the dynamics model catalyzer for olefinic polymerization is related to, this catalyzer can keep the polymerization efficiency of stable uniform in the scope of 50-90 DEG C, the molecular weight distribution of polymkeric substance can be made significantly to widen by alternating temperature operation.
Background technology
Poly molecular weight and molecualr weight distribution has important impact to the rheological property of its melt and the mechanical property of product.Polyethylene with wide molecular weight distribution is one of development field that polyethylene technology is important in recent years, different from common polythene material, polyethylene with wide molecular weight distribution not only can keep the mechanical property of High molecular weight polyethylene, hardness and environmental stress cracking resistance, and poly processing characteristics can be improved, wider molecular weight distribution can also make polyethylene melt have good mobility at higher shear rates, and this performance is very important for blowing and expressing technique.
At present, molecular weight of polyethylene and distribution thereof is regulated to mainly contain " Process " and " catalyst method ".
" Process " mainly uses different processing condition by different reactors, or utilizes multi-step polymerization process to obtain the polyethylene of wide molecular weight distribution, but production cost is high, and facility investment is large.Domestic and international many companies adopt this method to achieve the suitability for industrialized production of bimodal PE.
" catalyst method " is a kind of method comparatively simply regulating molecular weight of polyethylene distribution, mainly by changing traditional method for preparing catalyst and catalyzer moiety, prepare and direct production can have the catalyzer of the polythene material of wide molecular weight distribution, thus realize the polyethylene product becoming output wide molecular weight distribution in single reaction vessel.Consider from the angle of polymerization technique and polymer performance, in single reaction vessel, the polyethylene of production wide molecular weight distribution is ideal method.The method does not need to carry out large transformation to existing production equipment, existing many polyolefin devices can be upgraded easily and be produced High performance polyolefin product, reduced investment, instant effect, energy-saving and cost-reducing obviously, become current this area important development trend both domestic and external.
US5032562 and US5539076 discloses a kind of catalyzer producing bimodal high molecular weight polyethylene product, this catalyzer contains magnesium compound, zirconium compound (CpZrYnX2-n), titaniferous compound (TiCl4) or vanadium compounds and corresponding carrier, form Zr-Ti or the Zr-V catalyzer of compound, utilize the hydrogen regulation performance of two class active ingredients in catalyst system different, control the molecular weight distribution of product.Based on this technology, Univation company successfully develops the wide molecular weight distribution catalyzer that a kind of commodity are called Prodigy, and vapor phase process Unipol process unit successfully synthesizes bimodal high molecular weight polyethylene product.
CN1563114A has carrier and the titanium compound effect of different surfaces structure by two kinds, single tank ball milling is adopted to prepare the loaded catalyst with various active center, this catalyzer goes for multiple polymerization process, and processing parameter during by regulating the ratio of two kinds of carriers and being polymerized, obtain the polyethylene with wide molecular weight distribution of Mw/Mn more than 7, and molecular weight distribution can regulate.But what this method adopted is old-fashioned ball milled, and polymerization evaluation also only rests on reaction flask level.
CN1990509A and CN1827660A has prepared a kind of load type bimetallic polyethylene catalyst respectively, and the preparation method of this catalyzer first prepares the Z-N type active ingredient be carried on silicon-dioxide, then make its in aromatic hydrocarbons with non-luxuriant reaction.Described bimetallic catalyst coordinates with promotor and is used for ethylene polymerization, the polyethylene generated has wider molecular weight distribution, between 7-20, but the catalytic activity of this kind of catalyzer is lower, only has 400-1000g PE/g CAT, owing to have employed the organic precursors of more complicated, make preparation process complicated, preparation cost is high.
Summary of the invention
Object of the present invention is exactly provide a kind of in wider range of reaction temperature, all have olefin polymerization catalysis of stable reaction efficiency and its preparation method and application to overcome defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions: a kind of olefin polymerization catalysis, is characterized in that, this catalyzer is made up of body of catalyst component and promotor, and described body of catalyst component obtains by the following method:
(1), after organic-magnesium compound being reacted with hydroxy-containing compounds in carrier dispersing agent, add the compound with lone-pair electron and fully act on, then add titanium-containing compound and inert support, obtain suspension a;
(2), after organic-magnesium compound being reacted with hydroxy-containing compounds in carrier dispersing agent, add the compound with lone-pair electron and fully act on, then add vanadium-containing compound and inert support, obtain suspension b;
(3) suspension a mixes with suspension b, and adds active centre valence state conditioning agent, then distills drying, obtains body of catalyst component;
Described promotor is at least one general formula is AIR
5 xcl
3-xorgano-aluminium compound, wherein R
5, be the alkyl containing 1-18 carbon atom, wherein, x=1-3;
Wherein, the mol ratio of the aluminium content in promotor and body of catalyst knob part is (20-400): 1.
The structural formula of described organic-magnesium compound is MgR
1 ncl
2-n, R in formula
1the alkyl with 2-20 carbon atom, wherein n=1-2;
Described carrier dispersing agent is one or more in alkane compound;
The structure of described hydroxy-containing compounds is R
3oH, wherein R
3it is the alkyl containing 2-20 carbon atom
;
The described compound with lone-pair electron is one or more in ether, ester, amine, alcohol;
The structural formula of described titanium-containing compound is Ti (OR
2)
mcl
4-m, wherein R
2the alkyl wherein m=1-4 with 2-20 carbon atom;
Described vanadium-containing compound is VCl
3or VCl
4;
The structural formula of described active centre valence state conditioning agent is R
4 kalCl
3-k, wherein R
4the alkyl containing 1-14 carbon atom, k=0-3;
Described inert support is a kind of inert support had compared with large specific surface sum pore volume.
Described organic-magnesium compound is selected from dibutylmagnesium, diisobutyl magnesium, dioctyl magnesium, butyl octyl magnesium, ethyl-magnesium-chloride, the one in butyl magnesium chloride;
Described carrier dispersing agent is selected from one or more in normal hexane, hexanaphthene, Trimethylmethane, pentane, iso-pentane, hexane, hexanaphthene, heptane;
Described hydroxy-containing compounds is selected from the one in ethanol, propyl carbinol, n-propyl alcohol, Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol, Virahol, isopropylcarbinol, primary isoamyl alcohol, cyclopentanol, hexalin, vinyl carbinol, phenylcarbinol, benzhydrol, trityl alcohol, ethylene glycol, propylene glycol, glycerol, BDO;
The described compound with lone-pair electron is selected from one or more in diethyl ether, ethyl acetate, ethyl benzoate, tributyl phosphate, isopropylcarbinol, DMF first sulfoxide, thiophene, pyridine, picoline, piperazine, methylpiperazine, sec.-propyl piperazine;
Described titanium-containing compound is selected from the compound of the titaniums such as titanium tetrachloride, tetraethyl titanate, metatitanic acid n-propyl, isopropyl titanate, tetrabutyl titanate, tetramethoxy titanium, dimethoxy diethoxy titanium, purity titanium tetraethoxide, four titanium n-butoxide;
Described active centre valence state conditioning agent is selected from one or more in triethyl aluminum, tri-n-hexyl aluminum, diethyl aluminum chloride, ethylaluminum dichloride, di-isopropyl aluminum chloride, diisobutyl aluminum chloride, sesquialter ethylmercury chloride aluminium; Preferred triethyl aluminum, ethylaluminum dichloride.
Described inert support is selected from one or more in silicon-dioxide, aluminum oxide, titanium dioxide, silica-alumina, silica-magnesia, polynite.
Described inert support is heat-treated at 200-800 DEG C before using.
Step (1) and the middle compound adopted of step (2) can be the same or different;
The amount of each raw material used in the preparation of described body of catalyst component is: in every mole of organic-magnesium compound, titanium-containing compound is 0.01-1 mole, vanadium-containing compound 0.01-1 mole, hydroxyl compounds is 0.1-10 mole, inert support is 0.1-50 mole, the compound with lone-pair electron is 0.05-5 mole, active centre valence state conditioning agent 0.1-10 mole, and the consumption of carrier dispersing agent is the mass percent controlling solid matter in reaction system is 5-80%.
The amount of each raw material used in the preparation of described body of catalyst component is: in every mole of organic-magnesium compound, titanium-containing compound is 0.05-0.5 mole; Vanadium-containing compound 0.05-0.5 mole; Hydroxyl compounds is 0.5-5 mole; Inertia porosity is 2-20 mole; The compound with lone-pair electron is 0.2-2 mole; Active centre valence state conditioning agent is 0.1-1 mole, and the consumption of carrier dispersing agent is the mass percent controlling solid matter in reaction system is 15-60%.
In the preparation of described body of catalyst component, temperature of reaction is 10-100 DEG C, and the reaction times is 30 minutes-40 hours;
The temperature of described distillation drying is 20-90 DEG C, and the time is 30 minutes-40 hours.
In the preparation of described body of catalyst component, temperature of reaction is 30-80 DEG C, and the reaction times is 2 hours-15 hours;
The temperature of described distillation drying is 60-80 DEG C, and the time is 2 hours-15 hours.
A preparation method for olefin polymerization catalysis, is characterized in that, the method comprises the following steps:
(1) preparation of body of catalyst component:
A organic-magnesium compound is reacted with hydroxy-containing compounds by () in carrier dispersing agent after, add the compound with lone-pair electron and fully act on, then add titanium-containing compound and inert support, obtain suspension a;
B () adds the compound with lone-pair electron and fully acts on, then add vanadium-containing compound and inert support, obtain suspension b after organic-magnesium compound being reacted with hydroxy-containing compounds in carrier dispersing agent;
C () suspension a mixes with suspension b, and add active centre valence state conditioning agent, then distills drying, obtains body of catalyst component;
(2) preparation of catalyzer:
Be (20-400) by body of catalyst component and promotor according to the mol ratio of the aluminium content in promotor and body of catalyst component: 1 carry out used in combination.
Described catalyzer all can keep the polymerization efficiency of stable uniform the temperature range of 50-90 DEG C.
An application for olefin polymerization catalysis, is characterized in that, described catalyzer is suitable for but does not limit to the solution-air being applicable to alkene, the polymerization of gas-solid, gas-liquid-solid state.
An application for olefin polymerization catalysis, is characterized in that, described catalyzer carries out ethylene homo or ethene and alpha-olefin copolymer.
Compared with prior art, the present invention adopts a kind of catalyzer of dynamics model, this catalyzer all has stable reaction efficiency in wider range of reaction temperature, utilize catalyzer at differential responses temperature, be polymerized the feature producing differing molecular weight polymers, operated by alternating temperature, can be implemented in same reactor, produce the polyethylene product had compared with wide molecular weight distribution.
Accompanying drawing explanation
Fig. 1 is the molecular weight distribution curve of embodiment 11 polymerisate, and its molecular weight distribution is 6.25;
Fig. 2 is the molecular weight distribution curve of embodiment 12 polymerisate, and its molecular weight distribution is 6.30;
Fig. 3 is the molecular weight distribution curve of comparative example 6 polymerisate, and its molecular weight distribution is 4.30;
Fig. 4 is the molecular weight distribution curve of comparative example 7 polymerisate, and its molecular weight distribution is 4.28.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
The preparation of catalyzer
(1) under anhydrous and oxygen-free nitrogen protection, in the four-hole boiling flask of 250ml, add 100ml hexane, then add the hexane solvent containing 0.5 gram of dibutylmagnesium wherein; remaining under whipped state, adding 0.67 gram of ethanol, be heated to 70 DEG C; react 1 hour; then add 1.09 grams of ethyl benzoates, react 1 hour, then add 0.41 gram of titanium tetrachloride; react 2 hours; then add silicon-dioxide 4.35g, react 2 hours, obtain suspension a.
(2) under anhydrous and oxygen-free nitrogen protection, in the four-hole boiling flask of 250ml, add 100ml hexane, then add the hexane solvent containing 0.5 gram of dibutylmagnesium wherein; remaining under whipped state, adding 0.67 gram of ethanol, be heated to 70 DEG C; react 1 hour; then add 1.09 grams of ethyl benzoates, react 1 hour, then add 0.28 gram of vanadium tetrachloride; react 2 hours; then add silicon-dioxide 4.35g, react 2 hours, obtain suspension b.
(3) under anhydrous and oxygen-free nitrogen protection, in the four-hole boiling flask of 500ml, add suspension a and suspension b, remaining under whipped state; be heated to 70 DEG C, then add ethyl aluminum dichloride 1.9 grams, react after 3 hours; by the slurries evaporate to dryness obtained, obtain the host component of catalyzer.
The polymerization evaluation of catalyzer
In the reactor of 2 liters, add hexane 1200ml, triethyl aluminum 1.5ml, then add a certain amount of catalyzer, polymerizing condition is stagnation pressure 1.0MPa, wherein hydrogen partial pressure 0.2Mpa, ethylene partial pressure 0.8Mpa, is polymerized 4 hours at 50 DEG C.
Actually add catalyzer 0.0597g, obtain polyethylene 371g, catalytic efficiency is 6214g PE/g Cat.The density of polymkeric substance is 0.9522g/cm
3, melting index is 8.52 (21.6kg/10min).
Embodiment 2
The preparation of catalyzer is with embodiment 1; In polymerization appreciation condition, polymerization temperature is 60 DEG C, and other condition is with embodiment 1.
Actually add catalyzer 0.0548g, obtain polyethylene 319g, catalytic efficiency is 5821g PE/g Cat.The density of polymkeric substance is 0.9541g/cm
3, melting index is 12.48 (21.6kg/10min)
Embodiment 3
The preparation of catalyzer is with embodiment 1; In polymerization appreciation condition, polymerization temperature is 70 DEG C, and other condition is with embodiment 1.
Actually add catalyzer 0.0537g, obtain polyethylene 321g, catalytic efficiency is 5977g PE/g Cat.The density of polymkeric substance is 0.9550g/cm
3, melting index is 15.84 (21.6kg/10min)
Embodiment 4
The preparation of catalyzer is with embodiment 1; In polymerization appreciation condition, polymerization temperature is 80 DEG C, and other condition is with embodiment 1.
Actually add catalyzer 0.0561g, obtain polyethylene 347g, catalytic efficiency is 6185g PE/g Cat.The density of polymkeric substance is 0.9563g/cm
3, melting index is 17.65 (21.6kg/10min)
Embodiment 5
The preparation of catalyzer is with embodiment 1; In polymerization appreciation condition, polymerization temperature is 90 DEG C, and other condition is with embodiment 1.
Actually add catalyzer 0.0546g, obtain polyethylene 327g, catalytic efficiency is 5989g PE/g Cat.The density of polymkeric substance is 0.9577g/cm
3, melting index is 20.26 (21.6kg/10min)
Table one polymerization efficiency summary sheet
Embodiment 6
The preparation of catalyzer
(1) under anhydrous and oxygen-free nitrogen protection, in the four-hole boiling flask of 250ml, add 100ml heptane, add the heptane solvent containing 0.5 gram of dibutylmagnesium wherein; under the state remaining stirring, add 1.08 grams of butanols, be heated to 70 DEG C; react 1 hour; then add 0.97 gram of tributyl phosphate, react 1 hour, then add 0.27 gram of titanium tetrachloride; react 2 hours; then add silicon-dioxide 4.35g, react 2 hours, obtain suspension a.
(2) under anhydrous and oxygen-free nitrogen protection, in the four-hole boiling flask of 250ml, add 100ml heptane, then add the heptane solvent containing 0.5 gram of dibutylmagnesium wherein; under the state remaining stirring, add 1.08 grams of butanols, be heated to 70 DEG C; react 1 hour; then add 0.97 gram of tributyl phosphate, react 1 hour, then add 0.42 gram of vanadium tetrachloride; react 2 hours; then add silicon-dioxide 4.35g, react 2 hours, obtain suspension b.
(3) under anhydrous and oxygen-free nitrogen protection; suspension a and suspension b is added in the four-hole boiling flask of 500ml; under the state remaining stirring; be heated to 70 DEG C; then ethyl aluminum dichloride 1.9 grams is added; react 3 hours, the slurries evaporate to dryness then will obtained, obtains the host component of catalyzer.
In the reactor of 2 liters, add hexane 1200ml, hexene 50ml, triethyl aluminum 1.5ml, then add a certain amount of catalyzer, polymerizing condition is stagnation pressure 1.0MPa, wherein hydrogen partial pressure 2Mpa, ethylene partial pressure 08Mpa, is polymerized 4 hours at 50 DEG C.
Actually add catalyzer 0.0576g, obtain polyethylene 376g, catalytic efficiency is 6528g PE/g Cat.The density of polymkeric substance is 0.9435g/cm
3, melting index is 9.4 (21.6kg/10min)
Embodiment 7
The preparation of catalyzer is with embodiment 6; In polymerization appreciation condition, polymerization temperature is 60 DEG C, and other condition is with embodiment 6.
Actually add catalyzer 0.0522g, obtain polyethylene 335 grams, catalytic efficiency is 6417g PE/g Cat.The density of polymkeric substance is 0.9439g/cm
3, melting index is 18.39 (21.6kg/10min)
Embodiment 8
The preparation of catalyzer is with embodiment 6; In polymerization appreciation condition, polymerization temperature is 70 DEG C, and other condition is with embodiment 6.
Actually add catalyzer 0.0491g, obtain polyethylene 329g, catalytic efficiency is 6701g PE/g Cat.The density of its polymkeric substance is 0.9451g/cm
3, melting index is 38.74 (21.6kg/10min)
Embodiment 9
The preparation of catalyzer is with embodiment 6; In polymerization appreciation condition, polymerization temperature is 80 DEG C, and other condition is with embodiment 6.
Actually add catalyzer 0.0552g, obtain polyethylene 358g, catalytic efficiency is 6486g PE/g Cat.The density of its polymkeric substance is 0.94780g/cm
3, melting index is 46.52 (21.6kg/10min)
Embodiment 10
The preparation of catalyzer is with embodiment 6; In polymerization appreciation condition, polymerization temperature is 90 DEG C, and other condition is with embodiment 6.
Actually add catalyzer 0.0558g, obtain polyethylene 356g, catalytic efficiency is 6379g PE/g Cat.The density of its polymkeric substance is 0.9464g/cm
3, melting index is 98.35 (21.6kg/10min)
The polymerization efficiency summary sheet of table two embodiment
Embodiment 11
The preparation of catalyzer is with embodiment 1; In polymerization appreciation condition, alternating temperature controls polymerization temperature, and be first polymerized 1.5 hours at 55 DEG C, then temperature is adjusted to 85 DEG C of repolymerization 1.5 hours, other condition is with embodiment 1.
Actually add catalyzer 0.0543g, obtain polyethylene 283g, catalytic efficiency is 5211g PE/g Cat.The density of its polymkeric substance is 0.9548g/cm3, and melting index is 16.35 (21.6kg/10min).The molecular weight distribution of polymkeric substance is 6.25, and its curve is shown in Fig. 1.
Embodiment 12
The preparation of catalyzer is with embodiment 6; In polymerization appreciation condition, alternating temperature controls polymerization temperature, and be first polymerized 1.5 hours at 55 DEG C, then temperature is adjusted to 85 DEG C of repolymerization 1.5 hours, other condition is with embodiment 6.
Actually add catalyzer 0.0537g, obtain polyethylene 275g, catalytic efficiency is 5121g PE/g Cat.The density of its polymkeric substance is 0.9473g/cm3, and melting index is 38.35 (21.6kg/10min).The molecular weight distribution of polymkeric substance is 6.30, and its curve is shown in Fig. 2.
Comparative example 1
The preparation of catalyzer adopts conventional known magnesium Titanium series catalyst preparation method
(1) under nitrogen protection, in the four-hole boiling flask of 250mL, add 100ml hexane, then add the heptane solvent including 0.5 gram of dibutylmagnesium wherein; under whipped state, add 0.54 gram of butanols, be heated to 70 DEG C; react after 1 hour; add 0.48 gram of tributyl phosphate, react after 1 hour, add 0.27 gram of titanium tetrachloride; keep stirring 2 hours; then add silicon-dioxide 3.04g, keep stirring 2 hours, obtain suspension.
(2) under nitrogen protection, then add and ethyl aluminum dichloride 1.33 grams, react 3 hours, obtain suspension, evaporate to dryness, obtain catalyst component.
The appreciation condition of catalyzer is with embodiment 1.
Actually add catalyzer 0.0574g, obtain polyethylene 122g, catalytic efficiency is 2125g PE/g Cat.The density of its polymkeric substance is 0.9545g/cm
3, melting index is 7.63 (21.6kg/10min)
Comparative example 2
The preparation of catalyzer is with comparative example 1; During polymerization is evaluated, polymerization temperature is 60 DEG C, and other condition is with embodiment 1.
Actually add catalyzer 0.0545g, obtain polyethylene 175 grams, catalytic efficiency is 3211g PE/g Cat.The density of its polymkeric substance is 0.9534g/cm
3, melting index is 6.87 (21.6kg/10min)
Comparative example 3
The preparation of catalyzer is with comparative example 1; During polymerization is evaluated, polymerization temperature is 70 DEG C, and other condition is with embodiment 1.
Actually add catalyzer 0.0561g, obtain polyethylene 221g, catalytic efficiency is 3939g PE/g Cat.The density of its polymkeric substance is 0.9550g/cm
3, melting index is 13.73 (21.6kg/10min)
Comparative example 4
The preparation of catalyzer is with comparative example 1; During polymerization is evaluated, polymerization temperature is 80 DEG C, and other condition is with embodiment 1.
Actually add catalyzer 0.0582g, obtain polyethylene 297g, catalytic efficiency is 5103g PE/g Cat.The density of its polymkeric substance is 0.9541g/cm
3, melting index is 10.52 (21.6kg/10min)
Comparative example 5
The preparation of catalyzer is with comparative example 1; During polymerization is evaluated, polymerization temperature is 90 DEG C, and other condition is with embodiment 1.
Actually add catalyzer 0.0586g, obtain polyethylene 364g, catalytic efficiency is 6212g PE/g Cat.The density of its polymkeric substance is 0.9549g/cm
3, melting index is 8.74 (21.6kg/10min)
The polymerization efficiency summary sheet of table three comparative example
Comparative example 6
The preparation of catalyzer is with comparative example 1; Polymerization appreciation condition is with embodiment 11.
Actually add catalyzer 0.0528g, obtain polyethylene 170g, catalytic efficiency is 3220g PE/g Cat.The density of its polymkeric substance is 0.9538g/cm3, and melting index is 12.35 (21.6kg/10min).The molecular weight distribution of polymkeric substance is 4.30, and its curve is shown in Fig. 3.
Comparative example 7
The preparation of catalyzer is with comparative example 1; Polymerization appreciation condition is with embodiment 12.
Actually add catalyzer 0.0553g, obtain polyethylene 166g, catalytic efficiency is 3001g PE/g Cat.The density of its polymkeric substance is 0.9469g/cm3, and melting index is 36.2 (21.6kg/10min).The molecular weight distribution of polymkeric substance is 4.28, and its curve is shown in Fig. 4.
Above-mentioned catalyzer is suitable for but does not limit to the solution-air being applicable to alkene, the polymerization of gas-solid, gas-liquid-solid state.Described catalyzer can carry out ethylene homo or ethene and α-alkene alkene copolymerization.
Embodiment 13
A preparation method for olefin polymerization catalysis, the method comprises the following steps:
(1) preparation of body of catalyst component:
(a) by organic-magnesium compound butyl magnesium chloride 1mol in carrier dispersing agent normal hexane with hydroxy-containing compounds 1,4-butyleneglycol 0.1mol is after 10 DEG C of reaction 30min, add the compound thiophene 0.05mol with lone-pair electron fully to act on, titanium-containing compound dimethoxy diethoxy titanium 0.01mol and inert support polynite 0.1mol is added again at 10 DEG C, reaction 30min, obtains suspension a; The consumption of carrier dispersing agent is the mass percent controlling solid matter in reaction system is 5%.
B organic-magnesium compound butyl magnesium chloride 1mol is reacted 30min with hydroxy-containing compounds vinyl carbinol 0.1mol at 10 DEG C by () in carrier dispersing agent hexanaphthene after, add the compound thiophene 0.05mol with lone-pair electron fully to act on, vanadium-containing compound vanadium trichloride 0.01mol and inert support polynite 0.1mol is added again at 10 DEG C, reaction 30min, obtains suspension b; The consumption of carrier dispersing agent is the mass percent controlling solid matter in reaction system is 15%.
C () suspension a mixes with suspension b, and add active centre valence state conditioning agent triethyl aluminum 0.1mol, then at 20 DEG C of dry 40h of distillation, obtains body of catalyst component;
Described inert support is heat-treated at 200 DEG C before using.
(2) preparation of catalyzer:
By body of catalyst component and promotor according to the mol ratio of the aluminium content in promotor and body of catalyst component be 20: 1 carry out used in combination.
Described catalyzer all can keep the polymerization efficiency of stable uniform the temperature range of 50-90 DEG C.
Embodiment 14
A preparation method for olefin polymerization catalysis, the method comprises the following steps:
(1) preparation of body of catalyst component:
A organic-magnesium compound butyl octyl magnesium 1mol is reacted 40h with hydroxy-containing compounds propyl carbinol 10mol at 100 DEG C by () in carrier dispersing agent heptane after, add the compounds benzoic acid ethyl ester 5mol with lone-pair electron fully to act on, titanium-containing compound dimethoxy diethoxy titanium 1mol and inert support titanium dioxide 50mol is added again at 100 DEG C, reaction 40h, obtains suspension a; The consumption of carrier dispersing agent is the mass percent controlling solid matter in reaction system is 80%.
B organic-magnesium compound dioctyl magnesium 1mol is reacted 40h with hydroxy-containing compounds vinyl carbinol 10mol at 100 DEG C by () in sanction body dispersion agent heptane after, add the compounds benzoic acid ethyl ester 5mol with lone-pair electron fully to act on, vanadium-containing compound 1mol and inert support titanium dioxide 50mol is added again at 100 DEG C, reaction 40h, obtains suspension b; The consumption of carrier dispersing agent is the mass percent controlling solid matter in reaction system is 60%.
C () suspension a mixes with suspension b, and add active centre valence state conditioning agent di-isopropyl aluminum chloride 10mol, then at 90 DEG C of dry 30min of distillation, obtains body of catalyst component;
Described inert support is heat-treated at 800 DEG C before using.
(2) preparation of catalyzer:
By body of catalyst component and promotor according to the mol ratio of the aluminium content in promotor and body of catalyst component be 400: 1 carry out used in combination.
Described catalyzer all can keep the polymerization efficiency of stable uniform the temperature range of 50-90 DEG C.
Claims (12)
1. an olefin polymerization catalysis, is characterized in that, this catalyzer is made up of body of catalyst component and promotor, and described body of catalyst component obtains by the following method:
(1), after organic-magnesium compound being reacted with hydroxy-containing compounds in carrier dispersing agent, add the compound with lone-pair electron and fully act on, then add titanium-containing compound and inert support, obtain suspension a;
(2), after organic-magnesium compound being reacted with hydroxy-containing compounds in carrier dispersing agent, add the compound with lone-pair electron and fully act on, then add vanadium-containing compound and inert support, obtain suspension b;
(3) suspension a mixes with suspension b, and adds active centre valence state conditioning agent, then distills drying, obtains body of catalyst component;
Described promotor is at least one general formula is AlR
5 xcl
3-xorgano-aluminium compound, wherein R
5, be the alkyl containing 1-18 carbon atom, wherein, x=1-3;
Wherein, the aluminium content in promotor and the mol ratio of body of catalyst component are (20-400): 1.
2. a kind of olefin polymerization catalysis according to claim 1, is characterized in that, the structural formula of described organic-magnesium compound is MgR
1 ncl
2-n, R in formula
1the alkyl with 2-20 carbon atom, wherein n=1-2;
Described carrier dispersing agent is one or more in alkane compound;
The structure of described hydroxy-containing compounds is R
3oH, wherein R
3it is the alkyl containing 2-20 carbon atom;
The described compound with lone-pair electron is one or more in ether, ester, amine, alcohol;
The structural formula of described titanium-containing compound is Ti (OR
2)
mcl
4-m, wherein R
2the alkyl wherein m=1-4 with 2-20 carbon atom;
Described vanadium-containing compound is VCl
3or VCl
4;
The structural formula of described active centre valence state conditioning agent is R
4 kalCl
3-k, wherein R
4the alkyl containing 1-14 carbon atom, k=0-3;
Described inert support is a kind of inert support had compared with large specific surface sum pore volume.
3. a kind of olefin polymerization catalysis according to claim 1 and 2, is characterized in that, described organic-magnesium compound is selected from dibutylmagnesium, diisobutyl magnesium, dioctyl magnesium, butyl octyl magnesium, ethyl-magnesium-chloride, the one in butyl magnesium chloride;
Described carrier dispersing agent is selected from one or more in normal hexane, hexanaphthene, Trimethylmethane, pentane, iso-pentane, hexane, hexanaphthene, heptane;
Described hydroxy-containing compounds is selected from the one in ethanol, propyl carbinol, n-propyl alcohol, Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol, Virahol, isopropylcarbinol, primary isoamyl alcohol, cyclopentanol, hexalin, vinyl carbinol, phenylcarbinol, benzhydrol, trityl alcohol, ethylene glycol, propylene glycol, glycerol, BDO;
The described compound with lone-pair electron is selected from one or more in diethyl ether, ethyl acetate, ethyl benzoate, tributyl phosphate, isopropylcarbinol, DMF first sulfoxide, thiophene, pyridine, picoline, piperazine, methylpiperazine, sec.-propyl piperazine;
Described titanium-containing compound is selected from the compound of the titaniums such as titanium tetrachloride, tetraethyl titanate, metatitanic acid n-propyl, isopropyl titanate, tetrabutyl titanate, tetramethoxy titanium, dimethoxy diethoxy titanium, purity titanium tetraethoxide, four titanium n-butoxide;
Described active centre valence state conditioning agent is selected from one or more in triethyl aluminum, tri-n-hexyl aluminum, diethyl aluminum chloride, ethylaluminum dichloride, di-isopropyl aluminum chloride, diisobutyl aluminum chloride, sesquialter ethylmercury chloride aluminium;
Described inert support is selected from one in silicon-dioxide, aluminum oxide, titanium dioxide, silica-alumina, silica-magnesia, polynite or youngster's kind.
4. a kind of olefin polymerization catalysis according to claim 1 and 2, is characterized in that, described inert support is heat-treated at 200-800 DEG C before using.
5. a kind of olefin polymerization catalysis according to claim 1, it is characterized in that, the amount of each raw material used in the preparation of described body of catalyst component is: in every mole of organic-magnesium compound, titanium-containing compound is 0.01-1 mole, vanadium-containing compound 0.01-1 mole, hydroxyl compounds is 0.1-10 mole, inert support is 0.1-50 mole, the compound with lone-pair electron is 0.05-5 mole, active centre valence state conditioning agent 0.1-10 mole, the consumption of carrier dispersing agent is the mass percent controlling solid matter in reaction system is 5-80%.
6. a kind of olefin polymerization catalysis according to claim 5, is characterized in that, the amount of each raw material used in the preparation of described body of catalyst component is: in every mole of organic-magnesium compound, titanium-containing compound is 0.05-0.5 mole; Vanadium-containing compound 0.05-0.5 mole; Hydroxyl compounds is 0.5-5 mole; Inertia porosity is 2-20 mole; The compound with lone-pair electron is 0.2-2 mole; Active centre valence state conditioning agent is 0.1-1 mole, and the consumption of carrier dispersing agent is the mass percent controlling solid matter in reaction system is 15-60%.
7. a kind of olefin polymerization catalysis according to claim 1, is characterized in that, in the preparation of described body of catalyst component, temperature of reaction is 10-100 DEG C, and the reaction times is 30 minutes-40 hours;
The temperature of described distillation drying is 20-90 DEG C, and the time is 30 minutes-40 hours.
8. a kind of olefin polymerization catalysis according to claim 7, is characterized in that, in the preparation of described body of catalyst component, temperature of reaction is 30-80 DEG C, and the reaction times is 2 hours-15 hours;
The temperature of described distillation drying is 60-80 DEG C, and the time is 2 hours-15 hours.
9. a preparation method for olefin polymerization catalysis as claimed in claim 1, is characterized in that, the method comprises the following steps:
(1) preparation of body of catalyst component:
A organic-magnesium compound is reacted with hydroxy-containing compounds by () in carrier dispersing agent after, add the compound with lone-pair electron and fully act on, then add titanium-containing compound and inert support, obtain suspension a;
B () adds the compound with lone-pair electron and fully acts on, then add vanadium-containing compound and inert support, obtain suspension b after organic-magnesium compound being reacted with hydroxy-containing compounds in carrier dispersing agent;
C () suspension a mixes with suspension b, and add active centre valence state conditioning agent, then distills drying, obtains body of catalyst component;
(2) preparation of catalyzer:
Be (20-400) by body of catalyst component and promotor according to the mol ratio of the aluminium content in promotor and body of catalyst component: 1 carry out used in combination.
10. a kind of olefin polymerization catalysis according to claim 9, is characterized in that, described catalyzer all can keep the polymerization efficiency of stable uniform the temperature range of 50-90 DEG C.
The application of 11. 1 kinds of olefin polymerization catalysis as claimed in claim 1, is characterized in that, described catalyzer is suitable for but does not limit to the solution-air being applicable to alkene, the polymerization of gas-solid, gas-liquid-solid state.
The application of 12. 1 kinds of olefin polymerization catalysis as claimed in claim 1, is characterized in that, described catalyzer carries out ethylene homo or ethene and alpha-olefin copolymer.
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