CN104356264B - 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 catalyst, especially relate to the system of a kind of dynamics model catalyst for olefinic polymerization
Preparation Method, this catalyst can keep the polymerization efficiency of stable uniform in the range of 50-90 DEG C, can make polymerization by alternating temperature operation
The molecular weight distribution of thing is significantly widened.
Background technology
The rheological property of its melt and the mechanical property of product are had important by the molecular weight and molecualr weight distribution of polyethylene
Impact.Polyethylene with wide molecular weight distribution is one of development field that polyethylene technology is important in recent years, with common polyethylene material
Material difference, polyethylene with wide molecular weight distribution is possible not only to keep the mechanical property of High molecular weight polyethylene, hardness and resistance to environment to answer
Power cracking performance, and the processing characteristics of polyethylene can be improved, wider molecular weight distribution can also make polyethylene melt exist
Having preferable mobility under higher shear rate, this performance is very important for blowing and expressing technique.
At present, regulation molecular weight of polyethylene and distribution thereof mainly have " Process " and " catalyst method ".
" Process " mainly uses different process conditions by different reactors, or utilizes multi-step polymerization process
Obtaining the polyethylene of wide molecular weight distribution, but production cost is high, equipment investment is big.The most many companies use this method real
Show the industrialized production of bimodal PE.
" catalyst method " is a kind of method of relatively simple regulation molecular weight of polyethylene distribution, is mainly passed by change
The method for preparing catalyst of system and catalyst constituent, prepare and can be directly produced the polyethylene with wide molecular weight distribution
The catalyst of material, thus realize becoming the polyethylene product of output width molecular weight distribution in single-reactor.From polymerization technique
From the point of view of polymer performance, the polyethylene producing wide molecular weight distribution in single-reactor is ideal method.
The method need not carry out existing process units big transformation, and existing many polyolefin devices can be upgraded easily
Produce High performance polyolefin product, reduced investment, instant effect, energy-saving and cost-reducing substantially, become important both domestic and external of current this area
Exhibition trend.
US5032562 and US5539076 discloses a kind of catalyst producing bimodal high molecular weight polyethylene product, and this is urged
Agent contains magnesium compound, zirconium compound (CpZrYnX2-n), titaniferous compound (TiCl4) or vanadium compounds and corresponding carrier, is formed compound
Zr-Ti or Zr-V catalyst, the hydrogen regulation performance utilizing two class active components in catalyst system is different, control product point
Son amount distribution.Based on this technology, Univation company successfully develops the wide molecular weight distribution of a kind of trade name Prodigy and urges
Agent, successfully synthesizes bimodal high molecular weight polyethylene product on vapor phase method Unipol process unit.
CN1563114A has carrier and the titanium compound effect of different surfaces structure by two kinds, uses single tank ball milling system
The standby loaded catalyst with various active center, this catalyst goes for multiple polymerization process, and can be by adjusting
The technological parameter when ratio of two kinds of carriers of joint and polymerization, it is thus achieved that Mw/Mn polyethylene with wide molecular weight distribution more than 7, and point
Son amount distribution can regulate.But, the method uses old-fashioned ball-milling method, and is polymerized evaluation and also only resides within reaction bulb
Level.
CN1990509A and CN1827660A is prepared for a kind of load type bimetallic polyethylene catalyst, this catalyst respectively
Preparation method be first to prepare the Z-N type active component being carried on silicon dioxide, then make its in aromatic hydrocarbons with non-cyclopentadienyl reaction.Institute
Stating bimetallic catalyst and coordinate with promoter for ethylene polymerization, the polyethylene of generation has wider molecular weight and divides
Cloth, between 7-20, but the catalysis activity of this kind of catalyst is relatively low, and only 400-1000g PE/g CAT, owing to have employed
More complicated organic precursors so that preparation process is complicated, preparation cost is high.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and provide a kind of in wider reaction
Olefin polymerization catalysis of stable reaction efficiency and its preparation method and application it is respectively provided with in temperature range.
The purpose of the present invention can be achieved through the following technical solutions: a kind of olefin polymerization catalysis, it is characterised in that
This catalyst is made up of catalyst body component and promoter, and described catalyst body component is made by the following method
:
(1), after organic-magnesium compound being reacted with hydroxy-containing compounds in carrier dispersing agent, add and there are lone pair electrons
Compound fully acts on, and adds titanium-containing compound and inert carrier, obtains suspension a；
(2), after organic-magnesium compound being reacted with hydroxy-containing compounds in carrier dispersing agent, add and there are lone pair electrons
Compound fully acts on, and adds vanadium-containing compound and inert carrier, obtains suspension b；
(3) suspension a mixes with suspension b, and adds active center valence state regulator, and then distillation is dried, and is urged
Agent host component；
Described promoter be at least one formula be AIR5 xCl3-xOrgano-aluminum compound, wherein R5, for containing 1-18
The alkyl of individual carbon atom, wherein, x=1-3；
Wherein, the aluminum content in promoter is (20-400) with the mol ratio of catalyst body knob part: 1.
The structural formula of described organic-magnesium compound is MgR1 nCl2-n, R in formula1It is the alkyl with 2-20 carbon atom, its
Middle n=1-2；
Described carrier dispersing agent is one or more in alkane compound；
The structure of described hydroxy-containing compounds is R3OH, wherein R3It it is the alkyl containing 2-20 carbon atom；
The described compound with lone pair electrons is one or more in ether, ester, amine, alcohol；
The structural formula of described titanium-containing compound is Ti (OR2)mCl4-m, wherein R2It it is the alkyl with 2-20 carbon atom
Wherein m=1-4；
Described vanadium-containing compound is VCl3Or VCl4；
The structural formula of described active center valence state regulator is R4 kAlCl3-k, wherein R4Containing 1-14 carbon atom
Alkyl, k=0-3；
Described inert carrier is a kind of inert carrier with large specific surface area and pore volume.
Described organic-magnesium compound is selected from dibutylmagnesium, diisobutyl magnesium, dioctyl magnesium, butyl octyl magnesium, tonsilon
Magnesium, the one in butyl magnesium chloride；
Described carrier dispersing agent is selected from normal hexane, hexamethylene, iso-butane, pentane, isopentane, hexane, hexamethylene, heptane
In one or more；
Described hydroxy-containing compounds selected from ethanol, n-butyl alcohol, normal propyl alcohol, n-amyl alcohol, hexanol, n-heptanol, isopropanol,
Isobutanol, isoamyl alcohol, cyclopentanol, Hexalin, 1-propenol-3, benzyl alcohol, benzhydrol, tritanol., ethylene glycol, propylene glycol, third
One in triol, BDO；
The described compound with lone pair electrons selected from diethyl ether, ethyl acetate, ethyl benzoate, tributyl phosphate,
In isobutanol, DMF first sulfoxide, thiophene, pyridine, picoline, piperazine, methyl piperazine, isopropyl piperazine
One or more；
Described titanium-containing compound is selected from titanium tetrachloride, tetraethyl titanate, metatitanic acid n-propyl, isopropyl titanate, metatitanic acid just
The compound of the titaniums such as butyl ester, titanium tetramethoxide, dimethoxy diethoxy titanium, purity titanium tetraethoxide, four titanium n-butoxide；
Described active center valence state regulator is selected from triethyl aluminum, tri-n-hexyl aluminum, diethyl aluminum chloride, ethyl dichloro
Change one or more in aluminum, diisopropyl aluminum chloride, diisobutyl aluminum chloride, sesquialter ethylmercury chloride aluminum；Preferably triethyl aluminum,
Ethylaluminum dichloride.
Described inert carrier selected from silicon dioxide, aluminium oxide, titanium dioxide, silica-alumina, silicon dioxide-
One or more in magnesium oxide, montmorillonite.
Described inert carrier carries out heat treatment at 200-800 DEG C before using.
The compound used in step (1) and step (2) can be the same or different；
The amount of each raw material used in the preparation of described catalyst body component is: with every mole of organic-magnesium compound
Meter, titanium-containing compound is 0.01-1 mole, vanadium-containing compound 0.01-1 mole, and hydroxyl compounds is 0.1-10 mole, lazy
Property carrier is 0.1-50 mole, and the compound with lone pair electrons is 0.05-5 mole, active center valence state regulator 0.1-10
Mole, the consumption of carrier dispersing agent is that in control reaction system, the mass percent of solid matter is 5-80%.
The amount of each raw material used in the preparation of described catalyst body component is: with every mole of organic-magnesium compound
Meter, 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 electrons is 0.2-2 mole；Active center valence state regulator is 0.1-
1 mole, the consumption of carrier dispersing agent is that in control reaction system, the mass percent of solid matter is 15-60%.
In the preparation of described catalyst body component, reaction temperature is 10-100 DEG C, the response time be 30 minutes-40 little
Time；
The temperature that described distillation is dried is 20-90 DEG C, and the time is 30 minutes-40 hours.
In the preparation of described catalyst body component, reaction temperature is 30-80 DEG C, and the response time is 2 hours-15 hours；
The temperature that described distillation is dried is 60-80 DEG C, and the time is 2 hours-15 hours.
The preparation method of a kind of olefin polymerization catalysis, it is characterised in that the method comprises the following steps:
(1) preparation of catalyst body component:
A organic-magnesium compound is reacted with hydroxy-containing compounds in carrier dispersing agent by () after, add and there are lone pair electrons
Compound fully acts on, and adds titanium-containing compound and inert carrier, obtains suspension a；
B organic-magnesium compound is reacted with hydroxy-containing compounds in carrier dispersing agent by () after, add and there are lone pair electrons
Compound fully acts on, and adds vanadium-containing compound and inert carrier, obtains suspension b；
C () suspension a mixes with suspension b, and add active center valence state regulator, and then distillation is dried, and is urged
Agent host component；
(2) preparation of catalyst:
By catalyst body component and promoter rubbing according to the aluminum content in promoter and catalyst body component
You are (20-400) by ratio: 1 is used in mixed way.
Described catalyst all can keep the polymerization efficiency of stable uniform the temperature range of 50-90 DEG C.
The application of a kind of olefin polymerization catalysis, it is characterised in that described catalyst is suitable for but does not limit to and be applicable to alkene
Solution-air, state gas-solid, gas-liquid-solid polymerization.
A kind of application of olefin polymerization catalysis, it is characterised in that described catalyst carry out ethylene homo or ethylene and α-
Olefin-copolymerization.
Compared with prior art, the present invention uses the catalyst of a kind of dynamics model, and this catalyst is in wider reaction
It is respectively provided with stable reaction efficiency in temperature range, utilizes catalyst to be polymerized generation different molecular weight at a temperature of differential responses and gather
The feature of compound, is operated by alternating temperature, it is possible to achieve in same reactor, produces the polyethylene with wider molecular weight distribution
Product.
Accompanying drawing explanation
Fig. 1 is the molecular weight distribution curve of embodiment 11 polymerizate, and its molecular weight distribution is 6.25；
Fig. 2 is the molecular weight distribution curve of embodiment 12 polymerizate, and its molecular weight distribution is 6.30；
Fig. 3 is the molecular weight distribution curve of comparative example 6 polymerizate, and its molecular weight distribution is 4.30；
Fig. 4 is the molecular weight distribution curve of comparative example 7 polymerizate, and its molecular weight distribution is 4.28.
Detailed description of the invention
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
The preparation of catalyst
(1) under anhydrous and oxygen-free nitrogen is protected, in the four-hole boiling flask of 250ml, add 100ml hexane, add the most wherein
Enter the hexane solvent containing 0.5 gram of dibutylmagnesium, under remaining stirring, add 0.67 gram of ethanol, be heated to 70 DEG C,
React 1 hour, be subsequently adding 1.09 grams of ethyl benzoate, react 1 hour, add 0.41 gram of titanium tetrachloride, react 2 hours,
It is subsequently adding silicon dioxide 4.35g, reacts 2 hours, obtain suspension a.
(2) under anhydrous and oxygen-free nitrogen is protected, in the four-hole boiling flask of 250ml, add 100ml hexane, add the most wherein
Enter the hexane solvent containing 0.5 gram of dibutylmagnesium, under remaining stirring, add 0.67 gram of ethanol, be heated to 70 DEG C,
React 1 hour, be subsequently adding 1.09 grams of ethyl benzoate, react 1 hour, add 0.28 gram of vanadium tetrachloride, react 2 hours,
It is subsequently adding silicon dioxide 4.35g, reacts 2 hours, obtain suspension b.
(3) under anhydrous and oxygen-free nitrogen is protected, in the four-hole boiling flask of 500ml, add suspension a and suspension b, beginning
It is kept stirring for eventually under state, is heated to 70 DEG C, be subsequently adding ethyl aluminum dichloride 1.9 grams, after reacting 3 hours, the serosity that will obtain
It is evaporated, obtains the host component of catalyst.
The polymerization evaluation of catalyst
In the reactor of 2 liters, add hexane 1200ml, triethyl aluminum 1.5ml, be subsequently adding a certain amount of catalyst, poly-
Conjunction 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.
Being actually added into catalyst 0.0597g, obtain polyethylene 371g, catalytic efficiency is 6214g PE/g Cat.Polymer
Density be 0.9522g/cm3, melt index is 8.52 (21.6kg/10min).
Embodiment 2
The preparation of catalyst is with embodiment 1；In polymerization appreciation condition, polymerization temperature is 60 DEG C, the same embodiment of other condition
1。
Being actually added into catalyst 0.0548g, obtain polyethylene 319g, catalytic efficiency is 5821g PE/g Cat.Polymer
Density be 0.9541g/cm3, melt index is 12.48 (21.6kg/10min)
Embodiment 3
The preparation of catalyst is with embodiment 1；In polymerization appreciation condition, polymerization temperature is 70 DEG C, the same embodiment of other condition
1。
Being actually added into catalyst 0.0537g, obtain polyethylene 321g, catalytic efficiency is 5977g PE/g Cat.Polymer
Density be 0.9550g/cm3, melt index is 15.84 (21.6kg/10min)
Embodiment 4
The preparation of catalyst is with embodiment 1；In polymerization appreciation condition, polymerization temperature is 80 DEG C, the same embodiment of other condition
1。
Being actually added into catalyst 0.0561g, obtain polyethylene 347g, catalytic efficiency is 6185g PE/g Cat.Polymer
Density be 0.9563g/cm3, melt index is 17.65 (21.6kg/10min)
Embodiment 5
The preparation of catalyst is with embodiment 1；In polymerization appreciation condition, polymerization temperature is 90 DEG C, the same embodiment of other condition
1。
Being actually added into catalyst 0.0546g, obtain polyethylene 327g, catalytic efficiency is 5989g PE/g Cat.Polymer
Density be 0.9577g/cm3, melt index is 20.26 (21.6kg/10min)
Table one polymerization efficiency summary sheet
Embodiment 6
The preparation of catalyst
(1) under anhydrous and oxygen-free nitrogen is protected, in the four-hole boiling flask of 250ml, add 100ml heptane, be added thereto to contain
There is the heptane solvent of 0.5 gram of dibutylmagnesium, when remaining stirring, add 1.08 grams of butanol, be heated to 70 DEG C, instead
Answer 1 hour, be subsequently adding 0.97 gram of tributyl phosphate, react 1 hour, add 0.27 gram of titanium tetrachloride, react 2 hours, so
Rear addition silicon dioxide 4.35g, reacts 2 hours, obtains suspension a.
(2) under anhydrous and oxygen-free nitrogen is protected, in the four-hole boiling flask of 250ml, add 100ml heptane, add the most wherein
Enter the heptane solvent containing 0.5 gram of dibutylmagnesium, when remaining stirring, add 1.08 grams of butanol, be heated to 70
DEG C, to react 1 hour, be subsequently adding 0.97 gram of tributyl phosphate, react 1 hour, add 0.42 gram of vanadium tetrachloride, reaction 2 is little
Time, it is subsequently adding silicon dioxide 4.35g, reacts 2 hours, obtain suspension b.
(3) under anhydrous and oxygen-free nitrogen is protected, in the four-hole boiling flask of 500ml, add suspension a and suspension b, beginning
Under the state being kept stirring for eventually, it is heated to 70 DEG C, is subsequently adding ethyl aluminum dichloride 1.9 grams, react 3 hours, then will obtain
Serosity is evaporated, and obtains the host component of catalyst.
In the reactor of 2 liters, add hexane 1200ml, hexene 50ml, triethyl aluminum 1.5ml, be subsequently adding a certain amount of
Catalyst, polymerizing condition is stagnation pressure 1.0MPa, wherein hydrogen partial pressure 2Mpa, ethylene partial pressure 08Mpa, is polymerized 4 hours at 50 DEG C.
Being actually added into catalyst 0.0576g, obtain polyethylene 376g, catalytic efficiency is 6528g PE/g Cat.Polymer
Density be 0.9435g/cm3, melt index is 9.4 (21.6kg/10min)
Embodiment 7
The preparation of catalyst is with embodiment 6；In polymerization appreciation condition, polymerization temperature is 60 DEG C, the same embodiment of other condition
6。
Being actually added into catalyst 0.0522g, obtain polyethylene 335 grams, catalytic efficiency is 6417g PE/g Cat.Polymer
Density be 0.9439g/cm3, melt index is 18.39 (21.6kg/10min)
Embodiment 8
The preparation of catalyst is with embodiment 6；In polymerization appreciation condition, polymerization temperature is 70 DEG C, the same embodiment of other condition
6。
Being actually added into catalyst 0.0491g, obtain polyethylene 329g, catalytic efficiency is 6701g PE/g Cat.Its polymerization
The density of thing is 0.9451g/cm3, melt index is 38.74 (21.6kg/10min)
Embodiment 9
The preparation of catalyst is with embodiment 6；In polymerization appreciation condition, polymerization temperature is 80 DEG C, the same embodiment of other condition
6。
Being actually added into catalyst 0.0552g, obtain polyethylene 358g, catalytic efficiency is 6486g PE/g Cat.Its polymerization
The density of thing is 0.94780g/cm3, melt index is 46.52 (21.6kg/10min)
Embodiment 10
The preparation of catalyst is with embodiment 6；In polymerization appreciation condition, polymerization temperature is 90 DEG C, the same embodiment of other condition
6。
Being actually added into catalyst 0.0558g, obtain polyethylene 356g, catalytic efficiency is 6379g PE/g Cat.Its polymerization
The density of thing is 0.9464g/cm3, melt index is 98.35 (21.6kg/10min)
The polymerization efficiency summary sheet of table two embodiment
Embodiment 11
The preparation of catalyst is with embodiment 1；In polymerization appreciation condition, alternating temperature controls polymerization temperature, is first polymerized at 55 DEG C
1.5 hours, being then adjusted to 85 DEG C of repolymerization 1.5 hours, other condition is with embodiment 1.
Being actually added into catalyst 0.0543g, obtain polyethylene 283g, catalytic efficiency is 5211g PE/g Cat.Its polymerization
The density of thing is 0.9548g/cm3, and melt index is 16.35 (21.6kg/10min).The molecular weight distribution of polymer is 6.25,
Its curve is shown in Fig. 1.
Embodiment 12
The preparation of catalyst is with embodiment 6；In polymerization appreciation condition, alternating temperature controls polymerization temperature, is first polymerized at 55 DEG C
1.5 hours, being then adjusted to 85 DEG C of repolymerization 1.5 hours, other condition is with embodiment 6.
Being actually added into catalyst 0.0537g, obtain polyethylene 275g, catalytic efficiency is 5121g PE/g Cat.Its polymerization
The density of thing is 0.9473g/cm3, and melt index is 38.35 (21.6kg/10min).The molecular weight distribution of polymer is 6.30,
Its curve is shown in Fig. 2.
Comparative example 1
The preparation of catalyst uses conventional known magnesium Titanium series catalyst preparation method
(1) under nitrogen protection, in the four-hole boiling flask of 250mL, add 100ml hexane, be then added thereto to include
The heptane solvent of 0.5 gram of dibutylmagnesium, under stirring, adds 0.54 gram of butanol, is heated to 70 DEG C, after reacting 1 hour, adds
0.48 gram of tributyl phosphate, after reacting 1 hour, adds 0.27 gram of titanium tetrachloride, is kept stirring for 2 hours, is subsequently adding titanium dioxide
Silicon 3.04g, is kept stirring for 2 hours, obtains suspension.
(2) under nitrogen protection, it is subsequently adding and ethyl aluminum dichloride 1.33 grams, reacts 3 hours, obtain suspension, be evaporated,
Obtain catalytic component.
The appreciation condition of catalyst is with embodiment 1.
Being actually added into catalyst 0.0574g, obtain polyethylene 122g, catalytic efficiency is 2125g PE/g Cat.Its polymerization
The density of thing is 0.9545g/cm3, melt index is 7.63 (21.6kg/10min)
Comparative example 2
The preparation of catalyst is with comparative example 1；During polymerization is evaluated, polymerization temperature is 60 DEG C, and other condition is with embodiment 1.
Being actually added into catalyst 0.0545g, obtain polyethylene 175 grams, catalytic efficiency is 3211g PE/g Cat.Its polymerization
The density of thing is 0.9534g/cm3, melt index is 6.87 (21.6kg/10min)
Comparative example 3
The preparation of catalyst is with comparative example 1；During polymerization is evaluated, polymerization temperature is 70 DEG C, and other condition is with embodiment 1.
Being actually added into catalyst 0.0561g, obtain polyethylene 221g, catalytic efficiency is 3939g PE/g Cat.Its polymerization
The density of thing is 0.9550g/cm3, melt index is 13.73 (21.6kg/10min)
Comparative example 4
The preparation of catalyst is with comparative example 1；During polymerization is evaluated, polymerization temperature is 80 DEG C, and other condition is with embodiment 1.
Being actually added into catalyst 0.0582g, obtain polyethylene 297g, catalytic efficiency is 5103g PE/g Cat.Its polymerization
The density of thing is 0.9541g/cm3, melt index is 10.52 (21.6kg/10min)
Comparative example 5
The preparation of catalyst is with comparative example 1；During polymerization is evaluated, polymerization temperature is 90 DEG C, and other condition is with embodiment 1.
Being actually added into catalyst 0.0586g, obtain polyethylene 364g, catalytic efficiency is 6212g PE/g Cat.Its polymerization
The density of thing is 0.9549g/cm3, melt index is 8.74 (21.6kg/10min)
The polymerization efficiency summary sheet of table three comparative example
Comparative example 6
The preparation of catalyst is with comparative example 1；Polymerization appreciation condition is with embodiment 11.
Being actually added into catalyst 0.0528g, obtain polyethylene 170g, catalytic efficiency is 3220g PE/g Cat.Its polymerization
The density of thing is 0.9538g/cm3, and melt index is 12.35 (21.6kg/10min).The molecular weight distribution of polymer is 4.30,
Its curve is shown in Fig. 3.
Comparative example 7
The preparation of catalyst is with comparative example 1；Polymerization appreciation condition is with embodiment 12.
Being actually added into catalyst 0.0553g, obtain polyethylene 166g, catalytic efficiency is 3001g PE/g Cat.Its polymerization
The density of thing is 0.9469g/cm3, and melt index is 36.2 (21.6kg/10min).The molecular weight distribution of polymer is 4.28,
Its curve is shown in Fig. 4.
Above-mentioned catalyst is suitable for but does not limit to and be applicable to the solution-air of alkene, state gas-solid, gas-liquid-solid polymerization.Described catalysis
Agent can carry out ethylene homo or ethylene and α-alkene alkene copolymerization.
Embodiment 13
A kind of preparation method of olefin polymerization catalysis, the method comprises the following steps:
(1) preparation of catalyst body component:
(a) by organic-magnesium compound butyl magnesium chloride 1mol in carrier dispersing agent normal hexane with hydroxy-containing compounds Isosorbide-5-Nitrae-fourth
Glycol 0.1mol is after 10 DEG C of reaction 30min, and addition has the compound thiophene 0.05mol of lone pair electrons and fully acts on, then
10 DEG C add titanium-containing compound dimethoxy diethoxy titanium 0.01mol and inert carrier montmorillonite 0.1mol, react 30min,
Obtain suspension a；The consumption of carrier dispersing agent is that in control reaction system, the mass percent of solid matter is 5%.
(b) by organic-magnesium compound butyl magnesium chloride 1mol in carrier dispersing agent hexamethylene with hydroxy-containing compounds 1-propenol-3
0.1mol is after 10 DEG C of reaction 30min, and addition has the compound thiophene 0.05mol of lone pair electrons and fully acts on, then at 10 DEG C
Add vanadium-containing compound vanadium trichloride 0.01mol and inert carrier montmorillonite 0.1mol, react 30min, obtain suspension b；Carry
The consumption of body dispersant is that in control reaction system, the mass percent of solid matter is 15%.
C () suspension a mixes with suspension b, and add active center valence state regulator triethyl aluminum 0.1mol, then exists
20 DEG C of distillations are dried 40h, obtain catalyst body component；
Described inert carrier carries out heat treatment at 200 DEG C before using.
(2) preparation of catalyst:
By catalyst body component and promoter rubbing according to the aluminum content in promoter and catalyst body component
You are than being to be used in mixed way at 20: 1.
Described catalyst all can keep the polymerization efficiency of stable uniform the temperature range of 50-90 DEG C.
Embodiment 14
A kind of preparation method of olefin polymerization catalysis, the method comprises the following steps:
(1) preparation of catalyst body component:
(a) by organic-magnesium compound butyl octyl magnesium 1mol in carrier dispersing agent heptane with hydroxy-containing compounds n-butyl alcohol
10mol is after 100 DEG C of reaction 40h, and addition has the compounds benzoic acid ethyl ester 5mol of lone pair electrons and fully acts on, then 100
DEG C add titanium-containing compound dimethoxy diethoxy titanium 1mol and inert carrier titanium dioxide 50mol, react 40h, hanged
Supernatant liquid a；The consumption of carrier dispersing agent is that in control reaction system, the mass percent of solid matter is 80%.
(b) by organic-magnesium compound dioctyl magnesium 1mol cut out in body dispersant heptane with hydroxy-containing compounds 1-propenol-3
10mol is after 100 DEG C of reaction 40h, and addition has the compounds benzoic acid ethyl ester 5mol of lone pair electrons and fully acts on, then 100
DEG C add vanadium-containing compound 1mol and inert carrier titanium dioxide 50mol, react 40h, obtain suspension b；Carrier dispersing agent
Consumption is that in control reaction system, the mass percent of solid matter is 60%.
C () suspension a mixes with suspension b, and add active center valence state regulator diisopropyl aluminum chloride 10mol,
Then it is dried 30min 90 DEG C of distillations, obtains catalyst body component；
Described inert carrier carries out heat treatment at 800 DEG C before using.
(2) preparation of catalyst:
By catalyst body component and promoter rubbing according to the aluminum content in promoter and catalyst body component
You are than being to be used in mixed way at 400: 1.
Described catalyst all can keep the polymerization efficiency of stable uniform the temperature range of 50-90 DEG C.
Claims (9)
1. an olefin polymerization catalysis, it is characterised in that this catalyst is made up of catalyst body component and promoter,
Described catalyst body component prepares by the following method:
(1), after organic-magnesium compound being reacted with hydroxy-containing compounds in carrier dispersing agent, the chemical combination with lone pair electrons is added
Thing fully acts on, and adds titanium-containing compound and inert carrier, obtains suspension a；
(2), after organic-magnesium compound being reacted with hydroxy-containing compounds in carrier dispersing agent, the chemical combination with lone pair electrons is added
Thing fully acts on, and adds vanadium-containing compound and inert carrier, obtains suspension b；
(3) suspension a mixes with suspension b, and adds active center valence state regulator, and then distillation is dried, and obtains catalyst
Host component；
Described promoter be at least one formula be AlR5 xCl3-xOrgano-aluminum compound, wherein R5For former containing 1-18 carbon
The alkyl of son, wherein, x=1-3；
Wherein, the aluminum content in promoter is (20-400) with the mol ratio of catalyst body component: 1；
The structural formula of described organic-magnesium compound is MgR1 nCl2-n, R in formula1It is the 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 R3OH, wherein R3It it is the alkyl containing 2-20 carbon atom；
The described compound with lone pair electrons is selected from diethyl ether, ethyl acetate, ethyl benzoate, tributyl phosphate, isobutyl
In alcohol, N,N-dimethylformamide, first sulfoxide, thiophene, pyridine, picoline, piperazine, methyl piperazine, isopropyl piperazine one
Plant or several；
The structural formula of described titanium-containing compound is Ti (OR2)mCl4-m, wherein R2It is the alkyl with 2-20 carbon atom, wherein
M=1-4；
Described vanadium-containing compound is VCl3Or VCl4；
The structural formula of described active center valence state regulator is R4 kAlCl3-k, wherein R4It is the alkane containing 1-14 carbon atom
Base, k=0-3；
The amount of each raw material used in the preparation of described catalyst body component is: in terms of every mole of organic-magnesium compound, contain
Titanium compound is 0.01-1 mole, vanadium-containing compound 0.01-1 mole, and hydroxy-containing compounds is 0.1-10 mole, and inert carrier is
0.1-50 mole, the compound with lone pair electrons is 0.05-5 mole, active center valence state regulator 0.1-10 mole, carrier
The consumption of dispersant is that in control reaction system, the mass percent of solid matter is 5-80%；
In the preparation of described catalyst body component, reaction temperature is 10-100 DEG C, and the response time is 30 minutes-40 hours；
The temperature that described distillation is dried is 20-90 DEG C, and the time is 30 minutes-40 hours.
A kind of olefin polymerization catalysis the most according to claim 1, it is characterised in that described organic-magnesium compound is selected from two
Dibutyl magnesium, diisobutyl magnesium, dioctyl magnesium, butyl octyl magnesium, ethyl-magnesium-chloride, the one in butyl magnesium chloride；
Described carrier dispersing agent one in normal hexane, iso-butane, pentane, isopentane, hexane, hexamethylene, the heptane or
Several；
Described hydroxy-containing compounds is selected from ethanol, n-butyl alcohol, normal propyl alcohol, n-amyl alcohol, hexanol, n-heptanol, isopropanol, isobutyl
One in alcohol, isoamyl alcohol, cyclopentanol, Hexalin, ethylene glycol, propylene glycol, glycerol, 1,4-butanediol；
The described compound with lone pair electrons is selected from diethyl ether, ethyl acetate, ethyl benzoate, tributyl phosphate, isobutyl
In alcohol, N,N-dimethylformamide, first sulfoxide, thiophene, pyridine, picoline, piperazine, methyl piperazine, isopropyl piperazine one
Plant or several；
Described titanium-containing compound is selected from tetraethyl titanate, metatitanic acid n-propyl, isopropyl titanate or tetrabutyl titanate；
Described active center valence state regulator is selected from triethyl aluminum, tri-n-hexyl aluminum, diethyl aluminum chloride, ethyl dichloride
One or more in aluminum, diisopropyl aluminum chloride, diisobutyl aluminum chloride；
Described inert carrier is selected from silicon dioxide, aluminium oxide, titanium dioxide, silica-alumina, silica-zirconia
One or more in magnesium, montmorillonite.
A kind of olefin polymerization catalysis the most according to claim 1, it is characterised in that described inert carrier use before
200-800 DEG C carries out heat treatment.
A kind of olefin polymerization catalysis the most according to claim 1, it is characterised in that described catalyst body component
The amount of each raw material used in preparation is: in terms of every mole of organic-magnesium compound, titanium-containing compound is 0.05-0.5 mole；Containing vanadium
Compound 0.05-0.5 mole；Hydroxy-containing compounds is 0.5-5 mole；Inert carrier is 2-20 mole；There are lone pair electrons
Compound is 0.2-2 mole；Active center valence state regulator is 0.1-1 mole, and the consumption of carrier dispersing agent is for controlling reactant
In system, the mass percent of solid matter is 15-60%.
A kind of olefin polymerization catalysis the most according to claim 1, it is characterised in that described catalyst body component
In preparation, reaction temperature is 30-80 DEG C, and the response time is 2 hours-15 hours；
The temperature that described distillation is dried is 60-80 DEG C, and the time is 2 hours-15 hours.
6. the preparation method of an olefin polymerization catalysis as claimed in claim 1, it is characterised in that the method includes following
Step:
(1) preparation of catalyst body component:
A organic-magnesium compound is reacted in carrier dispersing agent by () with hydroxy-containing compounds after, add the chemical combination with lone pair electrons
Thing fully acts on, and adds titanium-containing compound and inert carrier, obtains suspension a；
B organic-magnesium compound is reacted in carrier dispersing agent by () with hydroxy-containing compounds after, add the chemical combination with lone pair electrons
Thing fully acts on, and adds vanadium-containing compound and inert carrier, obtains suspension b；
C () suspension a mixes with suspension b, and add active center valence state regulator, and then distillation is dried, and obtains catalyst
Host component；
(2) preparation of catalyst:
By catalyst body component and promoter according to the mol ratio of the aluminum content in promoter Yu catalyst body component
For (20-400): 1 is used in mixed way.
The preparation method of a kind of olefin polymerization catalysis the most according to claim 6, it is characterised in that described catalyst exists
The temperature range of 50-90 DEG C all can keep the polymerization efficiency of stable uniform.
8. the application of an olefin polymerization catalysis as claimed in claim 1, it is characterised in that described catalyst is applicable to alkene
The solution-air of hydrocarbon, state gas-solid, gas-liquid-solid are polymerized.
9. the application of an olefin polymerization catalysis as claimed in claim 1, it is characterised in that described catalyst carries out ethylene
Homopolymerization or ethylene and alpha-olefin copolymer.
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| CN107810057B (en) * | 2015-06-19 | 2021-06-04 | 沙特***石油公司 | Antifouling oligomerization catalyst system |
| US10730965B2 (en) * | 2015-12-30 | 2020-08-04 | Sabic Global Technologies B.V. | Process for making a solid catalyst component for ethylene polymerization and co-polymerization |
| CN107304235B (en) * | 2016-04-20 | 2020-04-10 | 中国石油天然气股份有限公司 | Preparation method of catalyst for preparing polyethylene with narrow molecular weight distribution |
| CN108264680B (en) * | 2016-12-30 | 2021-06-01 | 中国石油天然气股份有限公司 | Medium-density polyethylene resin and application thereof in waterproof barrier geomembrane |
| CN110105472B (en) * | 2018-02-01 | 2021-08-31 | 中国石油天然气股份有限公司 | Z-N catalyst, preparation method and application thereof |
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| CN102887967A (en) * | 2012-10-17 | 2013-01-23 | 上海化工研究院 | Composite catalyst for producing polyethylene with wide molecular weight distribution as well as production method and application thereof |
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| US5075271A (en) * | 1988-01-15 | 1991-12-24 | Mobil Oil Corporation | Olefin polymerization process for preparing high density or linear low density polymers of controlled molecular weight distribution |
| EP0518944B1 (en) * | 1990-03-07 | 1994-04-27 | Exxon Chemical Patents Inc. | 1-olefin (co)polymerization catalyst for production of resins with a broad range of molecular weight distribution |
| CN101659716A (en) * | 2002-02-14 | 2010-03-03 | 诺沃伦技术控股公司 | Solid catalytic component and catalytic system of the ziegler-natta type, process for their preparation and their use in the polymerisation of alk-1-enes |
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Address after: 200062 Shanghai city Putuo District Yunling Road No. 345 Patentee after: Shanghai Chemical Research Institute Co., Ltd. Patentee after: Shanghai Leader Catalyst Co., Ltd. Address before: 200062 Shanghai city Putuo District Yunling Road No. 345 Patentee before: Shanghai Research Institute of Chemical Industry Patentee before: Shanghai Leader Catalyst Co., Ltd. |