CN105732852B - Z-N catalyst - Google Patents
Z-N catalyst Download PDFInfo
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- CN105732852B CN105732852B CN201410757798.4A CN201410757798A CN105732852B CN 105732852 B CN105732852 B CN 105732852B CN 201410757798 A CN201410757798 A CN 201410757798A CN 105732852 B CN105732852 B CN 105732852B
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Abstract
The present invention relates to a kind of Z N catalyst, structural formula is Ti VMgnAl, wherein Ti is titanium compound, and V is vfanadium compound, and MgnAl is magnesium, aluminium complex carrier, ranging from the 0.05~5 of n.
Description
Technical field
The present invention relates to a kind of Z-N catalyst.
Background technology
Bimodal/polyethylene with wide molecular weight distribution well solved polyvinyl resin processing performance and mechanical and physical performance it
Between contradiction, therefore be widely used in the fields such as film, tubing.
The technology for preparing bimodal/polyethylene with wide molecular weight distribution generally has 3 kinds：Melt blending method, tandem reactor method (are divided
Section reaction method) and single reactor method (one section of reaction method).Melt blending method refers to being produced respectively in two reactors in parallel
Then they are carried out melt mixed by the polymer of larger, smaller relative molecular mass by a certain percentage, to control polymerization production
The relative molecular mass distribution of product.Tandem reactor method refers to controlling different polymerizations in two or more concatenated reactors
Condition (such as different polymerization temperatures, polymerization time, molecular weight regulator) and be made bimodal/polyethylene with wide molecular weight distribution
Method, the technology is more mature, at present domestic and international many company (such as Chevron Phillips, LyondellBasell, three wells
Oiling, Borealis etc.) use this method successfully to realize industrialized production.But there is production in above two method
Cost is higher, product is difficult to uniform, quality easily fluctuates, produces the shortcomings of control difficulty is big.
Single reactor method is the resin that bimodal or wide molecular weight distribution is produced in a reactor, so as to so that resin
Reach the mixing of superparticle grade, this method is the product of catalyst system and catalyzing innovation.Compared with tandem reactor technology, single reactor
Production technology has the following advantages：(1) investment is saved.Investment and production cost are compared with usual tandem reactor, can be saved
30%~40%.(2) simple for process, the easily-controlled operation of reactor.(3) relative molecular mass distribution of product is uniform, improves
The machinability of product.(4) bimodal products be can be obtained it is not necessary that the 2nd reactor is arranged so that the shutting down of device is more held
Easily.
Bimodal/wide molecule is made by using similar and different type catalyst in a reactor in single reactor method
Weight distribution polyethylene product, the technology need not carry out existing industrial installation big transformation, easy to implement and cost
It is relatively low, energy consumption, material consumption in bimodal/wide molecular weight distribution product process of production can be greatly lowered, therefore single reactor method becomes
Prepare the developing direction of bimodal/polyethylene with wide molecular weight distribution technology.
Bimodal PE is prepared using single reactor method, key technology is exactly to develop catalyst system.The catalyst of production PE has
Point of single-activity and double activated, but since single active catalyst can only obtain the PE of narrow ditribution, and double activated catalyst is then
The PE of bimodal distribution can be obtained, therefore single reactor method prepares PE and uses double activated catalyst.
WO9747682 produces bimodal PE using the mixed catalyst containing chromium and titaniferous in single reactor, is catalyzed with two kinds
The different proportion of agent controls PE relative molecular mass distributions；The mixed catalyst of high Ti/Gr can produce high melt flows speed
The double-peak high-density polytene of rate.
CN1292389A is used forms urging for the bimetallic active center having by metallocene catalyst and Titanium series catalyst
Change system, the wherein co-catalyst of metallocene catalyst use mixed type alkylaluminoxane.By adjusting the molar ratio of 2 kinds of metals
And the dosage of 2 kinds or two or more alkyl aluminum, the relative molecular mass and average molecular of polymer can be adjusted in very large range
Mass Distribution, to obtain the very wide vistanex of relative molecular mass distribution.
EP1153943 polymerize ethylene, is made by the way that the mixed catalyst containing chromium and titaniferous is supported on silica gel
Bimodal PE.
WO0183498 provides a catalyst system that can prepare bimodal PE, which includes a kind of organic metal
Catalyst such as (CpTiCl2)2(such as aikyiaiurnirsoxan beta, organic borofluoride are processed containing organic calorize for O and at least one activating agent
Close the soild oxide etc. of object) and another organo-metallic compound such as (C5H4CH3)2ZrCl2Deng.
KR42620 is same by the way that a kind of metallocene catalyst and a kind of non-cyclopentadienyl Ti metal composites to be supported on simultaneously
On carrier, a kind of complex catalyst system is made, then under the action of MAO, by the way that vinyl polymerization, bimodal distribution is made
PE。
Zr base catalyst is supported on the SiO containing Ti by EP8492942On, then under the action of MAO, by poly- to ethylene
It closes, bimodal PE can also be made.
US5614456 is simultaneously by a kind of non-metallocene catalyst (such as TiCl4) and MAO and another metallocene catalyst
(BuCp)2-ZrCl2It is combined with each other, by the catalytic polymerization to ethylene, has been similarly obtained the PE of bimodal distribution.
Although bimodal PE can be made using catalyst mixing method or double-metal composite catalyst in above-mentioned patent, there is
Following disadvantage：Two kinds of catalyst or metallic element influence each other, and catalyst activity is relatively low, and the PE grain sizes of generation are uneven, and
It is easily separated in storage and transportational process, and then cause product cut size distribution more uneven.
A kind of vfanadium compound is loaded to complex carrier by CN103254330A, CN201110391120 and CN102408504A
On MgnAl, and then it is catalyzed ethylene and alpha-olefin synthesizing polyethylene product, but the activity of catalyst is relatively low.
The present invention loads to titanium compound and vfanadium compound on complex carrier MgnAl, forms dynamics model, improves
The catalytic activity of above-mentioned vanadium series catalyst, and then prepare the broader polyethylene product of relative molecular weight distribution.
Invention content
The object of the present invention is to provide a kind of single reactors to produce bimodal and/or polyethylene with wide molecular weight distribution method.
Specifically, the present invention uses a kind of Z-N catalyst systems, it includes the organic of a kind of catalyst containing Z-N and aluminium
The co-catalyst of compound composition, the catalyst system are suitable for slurry method technique, ethylene or second are directly catalyzed in single reactor
Alkene synthesizes the polyethylene product of bimodal and/or wide molecular weight distribution with high alpha-olefin.
The Z-N catalyst systems include：
(1) a kind of Z-N catalyst, structural formula：Ti-VMg·nAl.
Wherein, Ti is titanium compound, and V is vfanadium compound, and MgnAl is magnesium, aluminium complex carrier, n ranging from 0.05~
5, preferably 0.1~2.0.
(2) co-catalyst being made of the organic compound of aluminium.
The co-catalyst includes：Trimethyl aluminium, MAO (methylaluminoxane), a chloro-di-isobutyl aluminum, triisobutyl
The one such or two or more mixture of aluminium, one aluminium ethide of dichloro, triethyl aluminum, aluminium diethyl monochloride, tri-n-hexyl aluminum,
The molar ratio of aluminium titanium is 10~300.
A kind of preparation method of Z-N catalyst of the present invention is as follows：
1. in mixed organic solvents, the Mg powder of activation is reacted with ether and aromatic hydrocarbon mixture, obtains organo-magnesium compound
(MOS), reaction temperature is 30~130 DEG C；In terms of every mole of magnesium, ether is ratio between each reactant：0.1~5.0 mole, virtue
Fragrant hydrocarbon is 0.5~15 mole.
2. magnesium, aluminium compound complex carrier, reaction temperature 10 is obtained by the reaction in MOS and aromatic ester, aromatic hydrocarbon, alkyl aluminum
~100 DEG C；In terms of every mole of magnesium, aromatic ester is ratio between each reactant：0.05~1.0 mole, aromatic hydrocarbon is 0.5~10
Mole, organo-aluminium is 0.1~5 mole.
3. magnesium, aluminium compound complex carrier are reacted with the mixture of titanium compound and vfanadium compound, Z-N catalysis is obtained
Agent, reaction temperature are 30~100 DEG C；Ratio between each reactant in terms of every mole of magnesium, titanium compound and vfanadium compound it is total
Amount is：0.01~0.2 mole.
The mixed organic solvents are alkane and aromatic hydrocarbon mixed solvent, and wherein alkane includes：Normal butane, a chlorine penta
Alkane, chloroform, a chlorobutane, hexane, heptane, octane, 1,2- dichloroethanes, three chlorobutanes；Aromatic hydrocarbon includes：Benzene, toluene, diformazan
Benzene, chlorobenzene, dichloro-benzenes, trichloro-benzenes, monochlorotoluene, dichlorotoleune, benzotrichloride.Alkane and aromatic hydrocarbon may each be therein one
Kind or two kinds of mixture.
The ether and aromatic hydrocarbon mixture, wherein ether include：Ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, two
Isobutyl ether, two n-amylethers, isoamyl ether, two octyl ethers, bisisooctyl ether, metopryl, methyl tertiary butyl ether(MTBE), ethyl tert-butyl ether (ETBE),
Tertiary butyl phenylate；Aromatic hydrocarbon includes：Benzene,toluene,xylene, chlorobenzene, dichloro-benzenes, trichloro-benzenes, dichlorotoleune, benzotrichloride, bromine
Benzene, dibromobenzene, tribromo-benzene, dibromomethylbenzene.Ether and aromatic hydrocarbon may each be one such or two kinds mixtures.
The aromatic ester includes：Methyl benzoate, ethyl benzoate, propyl benzoate, repefral, neighbour
Diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, adjacent benzene
The mixture of one or both of dioctyl phthalate di-isooctyl, diisooctyl phthalate.
The alkyl aluminum is a chloro-di-isobutyl aluminum, triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, dichloro one
The mixture of one or more of aluminium ethide, sesquialter aluminium ethide, tri-n-hexyl aluminum.
The titanium compound general formula is Ti (OR) aXb, and R is the aliphatic group or aryl of C1~C10 in formula, and X is halogen,
A is 0,1,2 or 3, and b is 1 to 4 integer, a+b=3 or 4.
The vfanadium compound is three halogenation vanadyl, alkoxy vanadyl, alcohol vanadyl, vanadyl acetylacetonate, four halogenations
Any one in vanadium, alkoxy vanadium, vanadium acetylacetonate.
The high alpha-olefin includes one kind in propylene, butene-1, hexene -1, octene-1, cyclopentadiene, cyclohexene
Or two or more mixture.
Advantageous effect：
The present invention provides a kind of NEW TYPE OF COMPOSITE carrier Z-N catalyst, pass through chemical reaction in catalyst preparation process
Complex carrier is directly formed, and is combined in a manner of chemical bonding, the different chemical environment in complex carrier surface causes difference
The formation in activated centre；This dynamics model catalyst system and catalyzing can directly synthesize bimodal and/or wide relative molecular weight in single anti-device
The complex carrier intensity of the polyolefin products of distribution, this catalyst is higher, non-breakable in polymerization process, finally makes polymer
The bulk density of product improves, and fine powder content is relatively low, is conducive to industrialized production；Meanwhile the activity of the catalyst is relatively high,
The cost of polymerization product can be reduced, production efficiency is improved.
Specific implementation mode
It is further illustrated the present invention by embodiment, but is not limited to following embodiment.
Embodiment 1
(1) catalyst preparation
The first step：Use N2Row's 2000mL reactors are blown, Mg powder 85.5g (3.5mol) is added, oil bath heating is warming up to 80
DEG C, keep 1h.0.1g iodine (I is added2), 2mL chlorobutanes and 36mL chlorobenzene mixed solvents is added after reacting 40min, reaction causes
Afterwards, start to stir, the mixture of 300mL ether and 96mL chlorobenzenes is added dropwise, reaction temperature is 90 DEG C, and about 60min is added dropwise.It
The mixture of 100mL ether and 38mL chlorobenzenes is added dropwise afterwards, then 600mL chlorobenzenes are added dropwise, about 90min is added dropwise.React 6h, drop
Temperature stops stirring, in N2The lower natural subsidence of protection, upper layer claret liquid is organo-magnesium compound (MOS), and wherein content of magnesium is
1.02mol/L。
Second step：Temperature of reactor is adjusted to 25 DEG C, in N2Under protection, 400mL MOS is taken to be added in reactor, started
The mixed solution of 6mL diethyl phthalates and 20mL heptane is added dropwise in stirring, and about 30min is added dropwise, and keeps 30min, drop
Add the mixed solution of 42mL benzotrichlorides and 60mL heptane, about 40min to be added dropwise, keeps 20min；Temperature of reactor is risen to
60 DEG C, 60min is reacted, stops stirring, product is washed with 800mL heptane, reactor is cooled to 25 DEG C, and two chloroethenes are added dropwise
Base aluminium 236mL, reactor are warming up to 45 DEG C, react 2h.With heptane wash 5 times, nitrogen protection is for use.
Third walks：By reactor temperature control at 25 DEG C, by 2.0mL TiCl4And 38mLVCl4CCl4(V's is a concentration of for solution
0.034g/mL) it is added to MgCl made of step2In the suspension of carrier, system is warming up to 60 DEG C, keeps 1h.It is cooling,
800mL hexanes washed once, and it is 1.05% to be dried to obtain Z-N catalyst 45.2g, Ti content, V content 2.67%, MgnAl
Middle n is 0.81.
(2) polymerisation
Row's 2L polymeric kettles are blown with nitrogen, 1000mL hexanes are added, start stirring, while the triethyl aluminum that 4mmol is added is total
The hexane solution of catalyst starts polymeric kettle and controls program, starts to warm up.It is added when temperature of reaction system rises to 80 DEG C
Ethylene is added after polymerization temperature reaches 81 DEG C in the hydrogen of 0.05MPa and 1 catalyst of embodiment of 40mg, and it is anti-to start polymerization
It answers, reaction pressure control is 1.0MPa.After 2 hours reaction time, stops that ethylene is added, start to cool down, pressure release discharging, dry production
Object, catalyst activity 13.8kgPE/gcat, polymer bulk density 0.40g/cm3, the molecular weight distribution mw/mn of polymer is
26, refer to table 1.
Embodiment 2
According to the operating process of embodiment 1, Mg powder is heated to 40 DEG C in the first step, obtains content of magnesium in MOS solution and is
0.96mol/l.Other operations are same as Example 1, and it is 1.01% to obtain catalyst 42.8g, Ti content, V content 2.89%,
N is 0.84 in MgnAl, catalyst activity 12.2kgPE/gcat, polymer bulk density 0.39g/cm3, the molecule of polymer
Amount distribution Mw/Mn is 27, refers to table 1.
Embodiment 3
According to the operating process of embodiment 1, an ether addition is 200mL in the first step, other operations and embodiment 1
Identical, it is 0.97% to obtain catalyst 47.2g, Ti content, V content 2.71%, and n is 0.91 in MgnAl, catalyst activity
14.5kgPE/gcat, polymer bulk density 0.43g/cm3, the molecular weight distribution mw/mn of polymer is 25, refers to table 1.
Embodiment 4
According to the operating process of embodiment 3, an ether addition is 200mL in the first step, and secondary ether addition is
200mL, other operations are same as Example 3, and it is 1.12% to obtain catalyst 45.1g, Ti content, V content 2.53%, Mg
N is 1.02 in nAl, catalyst activity 15.7kgPE/gcat, polymer bulk density 0.41g/cm3, the molecular weight point of polymer
Cloth Mw/Mn is 29, refers to table 1.
Embodiment 5
According to the operating process of embodiment 1, second step diethyl phthalate replaces with diisobutyl phthalate,
Other operations are same as Example 1, and it is 1.25% to obtain catalyst 48.9g, Ti content, V content 2.66%, and n is in MgnAl
0.94, catalyst activity 16.4kgPE/gcat, polymer bulk density 0.42g/cm3, the molecular weight distribution mw/mn of polymer
It is 28, refers to table 1.
Embodiment 6
According to the operating process of embodiment 5, the addition of second step diisobutyl phthalate is 12mL, other operations
Same as Example 5, it is 0.83% to obtain catalyst 48.5g, Ti content, V content 2.58%, and n is 0.94 in MgnAl, is urged
Agent activity 12.7kgPE/gcat, polymer bulk density 0.38g/cm3, the molecular weight distribution mw/mn of polymer is 27, in detail
It is shown in Table 1.
Embodiment 7
According to the operating process of embodiment 5, second step ethyl aluminum dichloride replaces with aluminium diethyl monochloride, other operations and reality
It is identical to apply example 5, it is 1.08% to obtain catalyst 46.7g, Ti content, V content 2.64%, and n is 0.85 in MgnAl, catalyst
Active 13.9kgPE/gcat, polymer bulk density 0.36g/cm3, the molecular weight distribution mw/mn of polymer is 24, refers to table
1。
Embodiment 8
According to the operating process of embodiment 7, the reaction temperature that aluminium diethyl monochloride is added in second step is 10 DEG C, other operations
Same as Example 7, it is 1.03% to obtain catalyst 42.9g, Ti content, V content 2.04%, and n is 0.71 in MgnAl, is urged
Agent activity 11.2kgPE/gcat, polymer bulk density 0.36g/cm3, the molecular weight distribution mw/mn of polymer is 25, in detail
It is shown in Table 1.
Embodiment 9
According to the operating process of embodiment 7, it is 320mL that aluminium diethyl monochloride, which is added, in second step, other operations and embodiment 7
Identical, it is 0.75% to obtain catalyst 42.7g, Ti content, V content 2.20%, and n is 1.35 in MgnAl, catalyst activity
9.2kgPE/gcat, polymer bulk density 0.35g/cm3, the molecular weight distribution mw/mn of polymer is 19, refers to table 1.
Embodiment 10
According to the operating process of embodiment 9, third walks reaction temperature and controls at 100 DEG C, other operations and 9 phase of embodiment
Together, it is 0.76% to obtain catalyst 40.7g, Ti content, V content 2.55%, and n is 2.47 in MgnAl, catalyst activity
8.7kgPE/gcat, polymer bulk density 0.35g/cm3, the molecular weight distribution mw/mn of polymer is 18, refers to table 1.
Embodiment 11
According to the operating process of embodiment 9, third walks reaction temperature control at 80 DEG C, and other operations are same as Example 9,
It is 1.04% to obtain Z-N catalyst 42.2g, Ti content, V content 2.87%, and n is 1.25 in MgnAl, catalyst activity
10.7kgPE/gcat, polymer bulk density 0.37g/cm3, the molecular weight distribution mw/mn of polymer is 24, refers to table 1.
Embodiment 12
According to the operating process of embodiment 9, third walks reaction temperature control at 30 DEG C, and other operations are same as Example 9,
It is 0.92% to obtain catalyst 39.8g, Ti content, V content 2.54%, and n is 1.43 in MgnAl, catalyst activity
11.3kgPE/gcat, polymer bulk density 0.34g/cm3, the molecular weight distribution mw/mn of polymer is 20, refers to table 1.
Embodiment 13
With the catalyst of embodiment 1, triethyl aluminum is replaced with into triisobutyl aluminium in polymerization process, other operations and is implemented
Example 1 is identical, catalyst activity 15.8kgPE/gcat, polymer bulk density 0.40g/cm3, the molecular weight distribution Mw/ of polymer
Mn is 27, refers to table 1.
Embodiment 14
With the catalyst of embodiment 1, hydrogen usage is down to 0.02MPa, other operations and 1 phase of embodiment in polymerization process
Together, catalyst activity 18.1kgPE/gcat, polymer bulk density 0.41g/cm3, the molecular weight distribution mw/mn of polymer is
21, refer to table 1.
Embodiment 15
With the catalyst of embodiment 1, the addition of triethyl aluminum is 6mmol in polymerization process, other operations and embodiment 1
It is identical, catalyst activity 15.6kgPE/gcat, polymer bulk density 0.39g/cm3, the molecular weight distribution mw/mn of polymer
It is 24, refers to table 1.
Embodiment 16
According to the operating process of embodiment 1, organic solvent chlorobutane replaces with 1,2- dichloroethanes, Qi Tacao in the first step
Make same as Example 1, it is 1.02% to obtain Z-N catalyst 38.9g, Ti content, and V content 2.69%, n is in MgnAl
0.8, catalyst activity 13.7kgPE/gcat, polymer bulk density 0.38g/cm3, the molecular weight distribution mw/mn of polymer is
22, refer to table 1.
Embodiment 17
According to the operating process of embodiment 1, ether is replaced with into n-butyl ether, other operations and 1 phase of embodiment in the first step
Together, it is 1.05% to obtain catalyst 43.2g, Ti content, V content 2.84%, and n is 0.85 in MgnAl, catalyst activity
15.4kgPE/gcat, polymer bulk density 0.40g/cm3, the molecular weight distribution mw/mn of polymer is 25, refers to table 1.
Embodiment 18
According to the operating process of embodiment 1, diisobutyl phthalate is replaced with into ethyl benzoate in second step,
Its operation is same as Example 1, and it is 0.96% to obtain catalyst 39.4g, Ti content, V content 2.82%, and n is in MgnAl
0.64, catalyst activity 12.7kgPE/gcat, polymer bulk density 0.34g/cm3, the molecular weight distribution mw/mn of polymer
It is 21, refers to table 1.
Embodiment 19
According to the operating process of embodiment 1, second step ethyl aluminum dichloride replaces with tri-n-hexyl aluminum, other operations and implementation
Example 1 is identical, and it is 0.94% to obtain catalyst 44.6g, Ti content, V content 2.85%, and n is 0.94 in MgnAl, and catalyst is lived
Property 10.3kgPE/gcat, polymer bulk density 0.33g/cm3, the molecular weight distribution mw/mn of polymer is 24, refers to table 1.
Embodiment 20
According to the operating process of embodiment 1, third is walked 2.5mL TiCl4And 26mLVCl4CCl4Solution (the concentration of V
For 0.034g/mL) it is added to MgCl made of upper step2The other operations of suspension of carrier are same as Example 1, are dried to obtain Z-
N catalyst 45.3g, Ti content is 1.85%, V content 2.01%, and n is 0.83 in MgnAl, catalyst activity
15.5kgPE/gcat, polymer bulk density 0.40g/cm3, the molecular weight distribution mw/mn of polymer is 27, refers to table 1.
Embodiment 21
(1) catalyst preparation
The first step：Use N2Row's reactor is blown, Mg powder 24.3g (1mol) is added, temperature is 10 DEG C, keeps 5h.0.05g is added
Iodine (I2), 0.5mL chlorobutanes and 0.5mL chlorobenzene mixed solvents is added after reacting 30min, reacts after causing, starts to stir, is added dropwise
The mixture of 10mL ether and 2.1mL chlorobenzenes, reaction temperature are 30 DEG C, and about 60min is added dropwise.6.8mL ether is added dropwise later
With the mixture of 3.2mL chlorobenzenes, then 45.4mL chlorobenzenes are added dropwise, about 90min is added dropwise.6h is reacted, stops stirring, in N2Under protection
Natural subsidence, upper layer claret liquid are organo-magnesium compound (MOS), and wherein content of magnesium is 0.51mol/L.
Second step：Temperature of reactor is adjusted to 10 DEG C, in N2Under protection, 400mL MOS is taken to be added in reactor, started
The mixed solution of 12mL diethyl phthalates and 36mL heptane is added dropwise in stirring, and about 30min is added dropwise, and keeps 5h, is added dropwise
The mixed solution of 57mL benzotrichlorides and 57mL heptane, about 40min are added dropwise, and keep 20min；10 DEG C of reaction temperature, reaction
5h stops stirring, is washed to product with heptane；Temperature of reactor control is 10 DEG C, and the hexane that ethyl aluminum dichloride is added dropwise is molten
Liquid 463.3mL (a concentration of 1.1mol/L of ethyl aluminum dichloride) reacts 5h.With heptane wash 5 times, nitrogen protection is for use.
Third walks：By reactor temperature control at 25 DEG C, by 1.32mL TiCl4And 45mLVCl4CCl4(V's is a concentration of for solution
0.034g/mL) it is added to MgCl made of step2In the suspension of carrier, system is warming up to 100 DEG C, keeps 1h.It is cooling, oneself
Alkane washed once, and it is 1.09% to be dried to obtain Z-N catalyst 30.2g, Ti content, V content 1.57%, and n is in MgnAl
5.02。
(2) polymerisation
Polymerisation, catalyst activity 9.5kgPE/gcat, polymer bulk density 0.32g/ are carried out according to embodiment 1
cm3, the molecular weight distribution mw/mn of polymer is 21, refers to table 1.
Embodiment 22
The first step：Use N2Row's reactor is blown, Mg powder 24.3g (1mol) is added, temperature is 100 DEG C, keeps 0.5h.It is added
0.5g iodine (I2), 5mL chlorobutanes and 5mL chlorobenzene mixed solvents is added after reacting 30min, reacts after causing, starts to stir, is added dropwise
The mixture of 500mL ether and 61.5mL chlorobenzenes, reaction temperature are 130 DEG C, and about 60min is added dropwise.340mL second is added dropwise later
The mixture of ether and 96.2mL chlorobenzenes, then 1361.3mL chlorobenzenes are added dropwise, about 90min is added dropwise.6h is reacted, stops stirring, in N2
The lower natural subsidence of protection, upper layer claret liquid is organo-magnesium compound (MOS), and wherein content of magnesium is 0.34mol/L.
Second step：Temperature of reactor is adjusted to 100 DEG C, in N2Under protection, takes 400mL MOS to be added in reactor, open
Beginning to stir, the mixed solution of 0.9mL diethyl phthalates and 3mL heptane is added dropwise, about 10min is added dropwise, and keeps 0.5h,
The mixed solution of 4.8mL benzotrichlorides and 6.2mL heptane is added dropwise, about 10min is added dropwise, and keeps 20min；By temperature of reactor
100 DEG C are risen to, 0.5h is reacted, stops stirring, product is washed with heptane, reactor is cooled to 25 DEG C, and two chloroethenes are added dropwise
The hexane solution 6.2mL (a concentration of 1.1mol/L of ethyl aluminum dichloride) of base aluminium, reactor are warming up to 100 DEG C, react 0.5h.With
Heptane wash 5 times, nitrogen protection is for use.
Third walks：By reactor temperature control at 25 DEG C, by 0.05mL TiCl4And 1.6mLVCl4CCl4Solution (the concentration of V
For 0.034g/mL) it is added to MgCl made of upper step2In the suspension of carrier, system is warming up to 30 DEG C, keeps 1h.Hexane is washed
It washs once, it is 0.12% to be dried to obtain Z-N catalyst 16.5g, Ti content, V content 0.31%, and n is 0.05 in MgnAl.
(2) polymerisation
Polymerisation is carried out according to embodiment 1, catalyst activity 3.3kgPE/gcat, polymer bulk density 0.30g/
cm3, the molecular weight distribution mw/mn of polymer is 18, refers to table 1.
Comparative example 1
According to CN103254330A preparation method synthetic catalysts：
The first step：Use N2Row's 1000mL reactors are blown, Mg powder 40.5g (1.76mol) is added, oil bath heating is warming up to 80
DEG C, keep 1h.0.05g iodine (I is added2), 1mL chlorobutanes and 18mL chlorobenzene mixed solvents is added after reacting 20min, reaction causes
Afterwards, start to stir, the mixture of 152mL ether and 48mL chlorobenzenes is added dropwise, rate of addition should ensure that reactor temperature is less than 90
DEG C, about 30min is added dropwise.The mixture of 50mL ether and 19mL chlorobenzenes is added dropwise later, then 300mL chlorobenzenes, about 75min is added dropwise
It is added dropwise.6h is reacted, cooling stops stirring, in N2The lower natural subsidence of protection, upper layer claret liquid is organo-magnesium compound
(MOS), wherein content of magnesium is 0.91mol/l.
Second step：Temperature of reactor is adjusted to 25 DEG C, in N2Under protection, takes 200mL (MOS) to be added in reactor, open
Beginning to stir, the mixed solution of 3mL diethyl phthalates and 10mL heptane is added dropwise, about 15min is added dropwise, and keeps 15min,
The mixed solution of 21mL benzotrichlorides and 30mL heptane is added dropwise, about 40min is added dropwise, and keeps 20min；By temperature of reactor liter
To 60 DEG C, 60min is reacted, stops stirring, product is washed with 300mL heptane, reactor is cooled to 25 DEG C, and dichloro is added dropwise
Aluminium ethide 118mL, reactor are warming up to 45 DEG C, react 2h.With heptane wash 5 times, stand overnight.
Third walks：Prepare 6mL VOCl3CCl4Solution, wherein vanadium a concentration of 0.034g/mL, it is under being stirred at room temperature that this is molten
Liquid is added to MgCl made of step2In the suspension of carrier, system is warming up to 60 DEG C, keeps 1h.Cooling, 100mL hexanes are washed
It washs primary, is dried to obtain vanadium catalyst 12.5g, content of vanadium 3.15%, n is 0.9 in MgnAl.
Polymerization evaluation, catalyst activity 8.5kgPE/gcat, polymer bulk density 0.38g/ are carried out according to embodiment 1
cm3, the molecular weight distribution of polymer is 21, refers to table 1.
Comparative example 2
According to the operating process of comparative example 1, Mg powder is heated to 40 DEG C in the first step, obtains content of magnesium in MOS solution
For 0.85mol/l.Other operations are same as Example 1, obtain vanadium catalyst 8.5g, content of vanadium 2.9%, and n is in MgnAl
0.8, catalyst activity 5.3kgPE/gcat, polymer bulk density 0.39g/cm3, the molecular weight distribution of polymer is 19, in detail
It is shown in Table 1.
Comparative example 3
According to the operating process of comparative example 1, ether addition is 100mL in the first step, other operations and embodiment 1
It is identical, obtain vanadium catalyst 10.5g, content of vanadium 3.2%, n is 1.0, catalyst activity 7.6kgPE/gcat in MgnAl, is gathered
Close object bulk density 0.40g/cm3, the molecular weight distribution of polymer is 21, refers to table 1.
Comparative example 4
Titanium series catalyst used in enchashment slurry method process units, Ti content 5.25%, by the converging operation of embodiment 1
Process carries out polymerisation.Row's 2L polymeric kettles are blown with nitrogen, 1000mL hexanes are added, start stirring, while being added the three of 2mmol
The hexane solution of aluminium ethide co-catalyst starts polymeric kettle and controls program, starts to warm up.When temperature of reaction system rises to 80 DEG C
The hydrogen and 15mg catalyst of 0.05MPa is added, after polymerization temperature reaches 81 DEG C, ethylene is added, starts polymerisation, reaction
Pressure control is 1.0MPa.After 2 hours reaction time, stops leading to ethylene, start to cool down, pressure release discharging, desciccate, catalyst
Active 34.7kgPE/gcat, polymer bulk density 0.30g/cm3, the molecular weight distribution of polymer is 6.1, refers to table 1.
1 embodiment polymerization catalyst result of table summarizes
From the data in the table, titanium compound and vfanadium compound are supported on complex carrier by the present invention simultaneously, are effectively carried
The high activity of catalyst broadens molecular weight distribution while ensureing polymer higher heap density, can be in single reactor
Develop bimodal/polyethylene with wide molecular weight distribution product.
Claims (6)
1. a kind of Z-N catalyst, structural representation formula is Ti-VMgnAl, wherein Ti is titanium compound TiCl4, V is vanadium chemical combination
Object VCl4, MgnAl be magnesium, aluminium complex carrier, ranging from the 0.1~5 of n；
The preparation method of the Z-N catalyst is as follows：
1. in mixed organic solvents, the Mg powder of activation is reacted with ether and aromatic hydrocarbon mixture, obtains organo-magnesium compound, reaction
Temperature is 30~130 DEG C；Ratio between each reactant in terms of every mole of magnesium, ether be 0.1~5.0 mole, aromatic hydrocarbon be 0.5~
15 moles；
2. the magnesium, aluminium complex carrier, reaction temperature is obtained by the reaction in organo-magnesium compound and aromatic ester, aromatic hydrocarbon, alkyl aluminum
It is 10~100 DEG C；Ratio between each reactant is in terms of every mole of magnesium, and aromatic ester is 0.05~1.0 mole, aromatic hydrocarbon 0.5
~10 moles, alkyl aluminum is 0.1~5 mole；
3. by the magnesium, aluminium complex carrier and TiCl4And VCl4Mixture reaction, obtain Z-N catalyst, reaction temperature 30
~100 DEG C；Ratio between each reactant is in terms of every mole of magnesium, TiCl4And VCl4Total amount be 0.01~0.2 mole.
2. Z-N catalyst according to claim 1, wherein ranging from the 0.1~2.0 of the n.
3. Z-N catalyst according to claim 1, wherein the ether is being selected from ether, di-n-propyl ether, diisopropyl ether, two just
Butyl ether, diisobutyl ether, two n-amylethers, isoamyl ether, two octyl ethers, bisisooctyl ether, metopryl, methyl tertiary butyl ether(MTBE), ethyl uncle
One or both of butyl ether, tertiary butyl phenylate.
4. Z-N catalyst according to claim 1, wherein the aromatic hydrocarbon is selected from benzene,toluene,xylene, chlorobenzene, two
One or both of chlorobenzene, trichloro-benzenes, dichlorotoleune, benzotrichloride, bromobenzene, dibromobenzene, tribromo-benzene, dibromomethylbenzene.
5. Z-N catalyst according to claim 1, wherein the aromatic ester be selected from methyl benzoate, ethyl benzoate,
Propyl benzoate, repefral, diethyl phthalate, n-butyl phthalate, phthalic acid two
One kind in isobutyl ester, di-n-octyl phthalate, diisooctyl phthalate, diisooctyl phthalate or two
Kind.
6. Z-N catalyst according to claim 1, wherein the alkyl aluminum is selected from a chloro-di-isobutyl aluminum, triethyl group
At least one of aluminium, triisobutyl aluminium, aluminium diethyl monochloride, one aluminium ethide of dichloro, sesquialter aluminium ethide, tri-n-hexyl aluminum.
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