CN104072646B - A kind of ethene gas-phase polymerization or copolymerization catalyst composition and preparation thereof and application - Google Patents
A kind of ethene gas-phase polymerization or copolymerization catalyst composition and preparation thereof and application Download PDFInfo
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Abstract
The present invention relates to ethene gas-phase polymerization or copolymerization catalyst composition and preparation thereof and application；It is dissolved in titanium compound, iron compound and magnesium compound in oxolane, make mother liquor；To join in mother liquor through Overheating Treatment and chemically treated modified silica support, return stirring 1 hour, being dried it with high pure nitrogen purging afterwards, the excessive oxolane of removing, the residue content of control oxolane accounts for 10～15wt% of products therefrom gross weight；The solids that will obtain, is suspended in lower paraffin hydrocarbon solvent, at room temperature carries out reduction treatment with one or more alkyl aluminum compounds, and the reduction treatment time is 30min, then is dried with high pure nitrogen purging, prepares carbon monoxide-olefin polymeric；When this catalyst is for vinyl polymerization especially gas fluidised bed polymerisation, it is shown that higher catalysis activity, can prepare the polyethylene product of wider molecular weight distribution or bimodal distribution, gained polyethylene product bulk density is high, fine powder is few.
Description
Technical field
The present invention relates to a kind of be applicable to the catalyst producing bimodal or broad peak distribution polyethylene single-reactor and preparation thereof
Method, is specifically related to a kind of bimetallic silica gel carrier catalyst composition being applicable to vinyl polymerization or combined polymerization and preparation side thereof
Method.
Background technology
Polyvinyl resin is one of four big synthetic resin, and high performance polyvinyl resin to have higher toughness, higher intensity
Higher environmental stress cracking resistance.The molecular weight improving polyethylene can make these performances correspondingly improve.But,
When the molecular weight of polymer increases, it will usually make the processing characteristics of this resin decline.By preparation, there is wide or bimodal point
The polymer of son amount distribution, is possible not only to keep the characteristic performance of high molecular weight resin, and can also improve the processability of resin
Energy.Therefore the research and development of bimodal molded breadth distribution polyethylene resins are current polyethylene production business's questions of common concern.This kind of
Typically having low-molecular-weight section and two peak types of HMW section on the molecular weight distribution curve of resin, low molecular weight part can carry
The processing characteristics of high resin, high molecular weight moieties then can improve the mechanical strength feature of resin.Current existing prepare wide
Or the method for Bi-modal polyethylene resin, substantially can be divided into following three classes:
(1) resin melting blending method.Will the resin of different molecular weight mix in the molten state, this method not only cost
Higher, and it is difficult to reach the complete homogeneous blend of resin thus the final performance that affects resin；
(2) carrying out stage feeding polymerization by multistage reactor, can obtaining more uniform resin, operation adjustment flexibility is relatively big,
But exist and affect efficiency and the high problem of cost；
(3) in single-reactor, use bimetallic or many metal active constituents catalyst, utilize the polymerization that they are had nothing in common with each other
Behavior, is directly produced the polyethylene of wide molecular weight distribution in single-reactor.
In general above-mentioned a kind of many metal active constituents catalyst of the third method exploitation is ideal and feasible side
Method.For example: Chinese patent CN88101779, CN1342716A disclose and a kind of produce the poly-of middle-molecular-weihydroxyethyl distribution polyethylene
Conjunction method, the method uses the catalyst system and catalyzing of Ti, V bimetallic active center, and Ti component uses and is supported on silica gel
TiCl4/MgCl2/THF/Al(n-C6H13)3Catalyst, V component uses the VCl that is supported on silica gel3/ THF/DEAC urges
Agent.Before polymerisation, two kinds of catalyst are mixed into Ti, V catalyst system, when this system is for vinyl polymerization,
Activity is 2400～3600 grams of polyethylene/mM (V+Ti)/hour/100psi ethene (5～70,000 gram gram (V+Ti)),
MI2.16It is 0.10～1.90, MFR 40～69.It is generally acknowledged that titanium catalyst produces the resin of Narrow Molecular Weight Distribution, and vanadium base is catalyzed
Agent produces the resin of wide molecular weight distribution, and this invention then uses above two components forming mixed catalyst simultaneously, thus produces
The resin of middle-molecular-weihydroxyethyl distribution.
Chinese patent CN1058601A, CN1478108A also disclose a kind of employing reduction vfanadium compound and organic oxygen-containing zirconium
The carbon monoxide-olefin polymeric that compound is deposited on active carrier material by co-impregnation, the ethene polymers being prepared by this catalyst has
Having wide molecular weight distribution, being especially distributed more is the component that molecular weight is higher.Although dividing of this catalyst resulting polymers
Son amount distribution is relatively wide, but its catalyst activity is on the low side.
Chinese patent CN101225129A discloses and uses two kinds of late transition metal iron, the composite catalyst of nickel composition for making
Standby bimodal polyethylene, but required co-catalyst is generally MAO, and the production cost causing bimodal polyethylene is higher.
The US 20050054519 and CN1678640A of Univation Technologies, CN1413222A,
In the US 20050003950 and US20040186251 of ExxonMobile, all use Ziegler-Natta catalyst and cyclopentadienyl gold
The compound mode of metal catalyst produces the polyvinyl resin of bimodal wide distribution in single-reactor.Permissible from above prior art
Finding out, the compound system of use Ziegler-Natta catalyst and metallocene can be produced bimodal width in single-reactor and divide
Cloth polyvinyl resin, but carefully analyze it finds that this catalyst system exists more serious problem.Typical bimodal width
The basic characteristics of distribution polyethylene resins are, low molecular weight part reduced branching degree is to improve drawing abillity, HMW
Part highly-branched degree is to improve the mechanical property of material.But Ziegler-Natta catalyst and the complex of metallocene catalyst
The polymer that obtains of system on the contrary, show as polymer low-molecular amount part highly-branched degree, high molecular weight moieties reduced branching degree,
This is because add hydrogen to make when polymerization polyethylene molecule quantitative change that metallocene catalyst synthesizes is very low, and metallocene
Catalyst is better than the copolymerization performance of Ziegler-Natta catalyst, thereby results in comonomer to low-molecular-weight one section.
Can be seen that from the catalyst disclosed in above-mentioned patent, although use two or more Ziegler-Natta type to be catalyzed
The dynamics model catalyst that agent component is formed can prepare wide distribution or bimodal distribution polyvinyl resin, but there are still work
The problem that property is on the low side, typically all below 100,000 gram gram metals；And for disclosed in Chinese patent CN88101779
Ti/V catalyst system, the molecular weight distribution of gained polyvinyl resin is also narrow, and its melt flow ratio (MFR) is 40～70.
It is an object of the present invention to the defect overcoming above-mentioned prior art to exist, propose the catalyst of a kind of dynamics model,
This catalyst includes Ti component and late transition metal iron component, when for vinyl polymerization, shows higher catalyst and lives
Property, and the polyvinyl resin of wider molecular weight distribution or bimodal distribution can be prepared.The present invention chooses and can produce low point
Sub-weight northylen and the late transition metal iron catalyst of copolymerization performance difference, be combined with existing Ziegler-Natta catalyst and be used for
The preparation of bimodal wide distribution polyethylene, solves low molecular weight part and the problem of a large amount of side chain occurs, can be in single reactor
Realize the production of the typical double-peak polyethylene of the high culture degree of low-molecular-weight reduced branching degree, HMW.
It is a further object to provide a kind of above-mentioned catalyst at the wide molecular weight distribution of preparation or bimodal distribution polyethylene
Application in polymerization.
Content of the invention
An object of the present invention is that Ziegler-Natta type Ti catalyst and late transition metal iron catalyst are supported on chlorine simultaneously
Changing on magnesium/silica complex carrier, using the method for dipping to prepare complex catalyst system, this system can for vinyl polymerization
To prepare bimodal wide distribution polyethylene resins.
Another object of the present invention is to use the composite catalyzing of Ziegler-Natta type Ti catalyst/late transition metal iron catalyst
Agent system produces the method for typical double-peak width distribution polyethylene resins in single reactor.
The composite catalyst of Ziegler-Natta type Ti catalyst/late transition metal iron catalyst of the present invention refer to by
Ziegler-Natta type Ti catalyst and late transition metal iron catalyst complex load to magnesium chloride/silica in proportion and are combined
Obtain composite catalyst on carrier.Above-mentioned composite catalyst forms complex catalyst system together with co-catalyst.
For realizing the purpose of described invention, the technical solution used in the present invention is: provide a kind of bimetallic ethylene rolymerization catalyst
Composition, this catalyst is by catalyst carrier and the titaniferous, iron-containing catalyst active component and the co-catalysis that are supported on carrier
Agent forms, and described catalyst carrier is thermally treated and the chemically treated silica of alkyl aluminum, and described silica is
Spherical or class is spherical, its average grain diameter is 10～100 μm, specific surface area 250～800m2/g；Described titaniferous, iron content are catalyzed
Agent active component includes at least one titanium compound, at least one iron complex, at least one magnesium compound and at least one electricity
The back flow reaction product of sub-donor, described co-catalyst is alkyl aluminum compound.
The structure of described late transition metal complex is shown in formula I:
The structure of I iron complex
Wherein: R1～C3For alkyl, alkoxyl, phenoxy group, benzyl, halogen etc.；M is Fe.Metal shown in formula I is joined
The synthesis of compound is standby according to W09827124, W09830612 patent system.
In the late transition metal catalyst of load, the weight content of central metal M is generally 0.01～5%, and preferably 0.1～1
%.
Described magnesium compound is MgCl2、MgBr2、MgI2Or its mixture.
Described titanium compound is Ti (OR)4-nXn or TiX3, in formula, R is C1～C3Aliphatic group, X be F, Cl,
One or more of Br, n is the integer of 1～4.
Described electron donor is oxolane.
The formula of described alkyl aluminum compound is AlRmX3-m, R is C that is identical or that differ1-8Alkyl, X is halogen,
M is the integer of 1～3.
Described alkyl aluminum compound is AlEt3、Al(iso-Bu)3、Al(n-C6H13)3、Al(n-C8H17)3、AlEt2In Cl
The mixture of one or more.
Described silica is modified processing as follows:
(1) silica is placed in gas-phase fluidized-bed activator, blows fluidisation with nitrogen anhydrous, anaerobic, progressively heat up
To 200～700 DEG C, constant temperature is dehydrated 4～10 hours, prepares dehydrated silica；
(2) adding alkane solvent in dehydrated silica, the addition of solvent is 10mL/g SiO2, and add alkyl gold
Belonging to the hydroxyl on compound treatment surface, described alkyl metal cpd is alkyl aluminum, and the weight ratio of its consumption is that: A1/Si is
0.05～0.1:1, stirs 1～4 hour under room temperature, and heating makes alkane solvent evaporate, and the temperature of evaporation is 20～30 DEG C, is had
There is the activated silica of mobility；
Another technical scheme of the present invention is to provide the preparation method of described ethylene polymerization catalyst composition, and its step is such as
Under:
(1) it is dissolved in titanium compound, iron complex and magnesium compound in oxolane, wherein selection titanium trichloride: iron network
Compound: magnesium chloride: oxolane=1:0.5:3.15:247, temperature rising reflux reacts, makes mother liquor, wherein titanium compound, iron network
Compound joined before or after magnesium compound in oxolane or is simultaneously introduced both；Magnesium compound and iron compound
Weight is than for 100:1～1:1；The weight of oxolane and iron compound is than for 10000:1～1:1；
(2) by described be modified process after silica supports join in mother liquor prepared by (1) step, after to its with height
Pure nitrogen gas purging is dried, the excessive oxolane of removing, and controlling its residue content is 10～16 wt%；
(3) solids obtaining step (2), is suspended in lower paraffin hydrocarbon solvent, with one or more alkyl aluminum chemical combination
Thing at room temperature carries out reduction treatment, and in activation process, the addition of alkyl aluminum is: n(Al)/n (THF)=0.65, also original place
The reason time is 30min, then is dried with high pure nitrogen purging, prepares described carbon monoxide-olefin polymeric.
Described lower paraffin hydrocarbon solvent is isopentane, pentane or hexane.
Compared with prior art, beneficial effects of the present invention shows themselves in that
Catalyst system of the present invention has good ethylene homo and co-polymeric activity, the molecular weight of polyethylene obtaining
Distribution is in bimodal distribution.Bimodal polyethylene resins obtained by the present invention has low molecular weight part reduced branching degree, HMW
The feature of part highly-branched degree.In addition, the double-metal composite catalyst of the present invention can use a kind of co-catalyst, this also solves
The problem that in existing double-metal composite catalyst technology of having determined, required two kinds of co-catalysts interfere.
Ti/Fe complex catalyst system of the present invention obtains resin for vinyl polymerization and has good particle shape, permissible
It is applicable to slurry process and vapor phase method polymerization technique.
Detailed description of the invention
The vinyl polymerization bimetallic catalyst composition of the present invention is primarily adapted for use in ethene gas-phase polymerization or combined polymerization, and it is by being catalyzed
Agent carrier, Ti/Fe bimetallic active component and co-catalyst composition.Wherein, improved silica is catalyst carrier；Double gold
Belong to Ti/Fe active component be one include at least one titanium compound, at least one iron complex, at least one magnesium compound and
The back flow reaction product of at least one electron donor；Co-catalyst is alkyl aluminum.
Yet other embodiments be the average grain diameter of silica used be l0～100 μm, be preferably
15～50 μm, specific surface area is 280～700m2, preferably 400～600m2/ g, specific surface area is too small can affect active component
Load capacity.In addition, the present invention uses the following step to be modified to silica supports processing: silica is placed in by (1)
In gas-phase fluidized-bed activator, blow fluidisation with nitrogen anhydrous, anaerobic, be progressively warming up to 200～700 DEG C, be preferably
500～700 DEG C, constant temperature is dehydrated 4～10 hours.(2) dehydrated silica adds alkane solvent, and add metal alkyl
Compound processes surface, stirs 1～4 hour under room temperature, and heating makes alkane solvent evaporate, and obtains mobility and preferably activates dioxy
SiClx.The preferred alkyl aluminum of alkyl metal cpd of activation, the most handy triethyl aluminum, the weight ratio of its consumption is: A1/Si
=0.05～0.1:1.
Presently preferred embodiment is the method preparing described carbon monoxide-olefin polymeric: by described titanium compound,
Iron complex and magnesium compound are dissolved in electron donor, are prepared as mother liquor, are then supported at modification by the method for dipping
On silica-gel carrier after reason, the step that more preferred method is used is as follows:
(1) be dissolved in titanium compound, iron complex and magnesium compound in oxolane, make mother liquor, wherein titanium compound,
Iron complex can join before or after magnesium compound in oxolane or both and to be simultaneously introduced；
(2) by described be modified process after silica-gel carrier join in the mother liquor of (1) step, the back flow reaction regular hour
After, it being dried, the excessive oxolane of removing, general control residue content is at 10～16wt%；
(3) solids obtaining step (2), is suspended in lower paraffin hydrocarbon solvent, with one or more alkyl aluminum chemical combination
Thing carries out reduction treatment, more i.e. prepares final catalyst activity component after being dried.Wherein lower alkyl described in step (3)
Hydrocarbon solvent is C3～C9Alkane, preferably C5And C6Alkane, such as isopentane, pentane, hexane etc.；Described alkyl calorize
The formula of compound is AlRmX3-m, R is C that is identical or that differ1-8Alkyl, X is halogen, and m is the integer of 1～3,
Preferably AlEt3、Al(n-C6H13)3、AlEt2Cl etc..
The catalyst that the present invention relates to is applicable to the combined polymerization of all polymerization or ethene and other alpha-olefins of various ethene, wherein α-
Alkene is selected from propylene, butylene, amylene, hexene, octene, the one in 4-methylpentene-1.Its polymerization technique uses gas
Xiang Fa, slurry process and solwution method, be more suitable for gas fluidised bed polymerisation, particularly gas-phase fluidized-bed condensation technology.
Embodiment 1
The preparation of bimetallic catalyst composition:
(1) (Grace company of the U.S. produces, and average grain diameter is 45 μm, and specific surface area is 350m to weigh 20g spherical silica gel2/ g),
Silica is placed in gas-phase fluidized-bed activator, blows fluidisation with nitrogen anhydrous, anaerobic, be progressively warming up to 600 DEG C,
Constant temperature is dehydrated 6 hours, prepares dehydrated silica.
(2) in the reaction bulb of belt stirrer under nitrogen protection, add 100mL isopentane, (1) step will be lived through heat
Silica gel 10g after change process and the AlEt that 5.6mL concentration is 1mmol/mL3Hexane solution add, 20～30 DEG C of reactions
1 hour, heating made alkane solvent evaporate, and obtains the activated silica with mobility.
(3) in the reaction bulb of another belt stirrer, 0.64mL TiCl is added4, 2,6-double [1-(2,6-dimethyl benzene imines)
Ethyl] pyridyl iron dichloride 0.0968g, 1.74g MgCl2With 174mL oxolane, temperature rising reflux stirs 5 hours, i.e. makes
Obtain catalyst mother liquor.
(4) the mother liquor mixing that will be modified the silica gel handled well in (2nd) step and prepared by (3rd) step, return stirring 1 is little
When, it is then dried with high pure nitrogen purging, obtain mobility faint yellow solid powder, wherein the content of oxolane is
11.94Wt%。
(5) with isopentane as solvent under room temperature, AlEt is used2Cl and Al (n-C6H13)3Reaction to step (4) gained is produced
Thing carries out prereduction, and the recovery time is 30min, controls AlEt2The mol ratio of Cl/THF is 0.45:1, Al (n-C6H13)3/THF
For 0.20:1.Reaction is dried by high pure nitrogen purging after completing, and obtains slightly yellow solid powdery catalytic component.Its catalyst
In composition: Ti%=1.26Wt%, Fe%=0.08Wt%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out ethene slurry polymerization evaluation in 2L stainless steel cauldron, the consumption 50mg of catalyst,
H2/C2H4The AlEt of=0.28/0.75,1mL3Hexane solution (1mmol/mL), 1L hexane, 80 DEG C are reacted 2 hours.Urge
The synthesis condition of agent is shown in Table 1, and slurry polymerization the results are shown in Table 2.
Embodiment 2
The preparation of bimetallic catalyst composition:
(1) (Grace company of the U.S. produces, and average grain diameter is 45 μm, and specific surface area is to weigh about 20g spherical silica gel
350m2/ g), silica is placed in gas-phase fluidized-bed activator, blows fluidisation with nitrogen anhydrous, anaerobic, progressively heat up
To 600 DEG C, constant temperature is dehydrated 4 hours, prepares dehydrated silica.
(2) in the reaction bulb of belt stirrer under nitrogen protection, add 100mL isopentane, (1) step will be lived through heat
Silica gel 10g after change process and the AlEt that 5.6mL concentration is 1mmol/mL3Hexane solution add, 20～30 DEG C of reactions
1 hour, heating made alkane solvent evaporate, and obtains the activated silica with mobility.
(3) in the reaction bulb of another belt stirrer, 0.64mL TiCl is added4, 2,6-double [1-(2,6-dimethyl benzene imines)
Ethyl] pyridyl iron dichloride 0.1937g, 1.74g MgCl2With and 174mL oxolane, temperature rising reflux stir 5 hours, i.e.
Prepare catalyst mother liquor.
(4) the mother liquor mixing prepared good silica gel chemically treated in (2nd) step and (3rd) step, return stirring 1 is little
When, it is then dried with high pure nitrogen purging, obtain mobility faint yellow solid powder, wherein the content of oxolane is
11.80Wt%。
(5) with isopentane as solvent under room temperature, AlEt is used2Cl and Al (n-C6H13)3Reaction to step (4) gained is produced
Thing carries out prereduction, and the recovery time is 30min, controls AlEt2The mol ratio of Cl/THF is 0.45:1, Al (n-C6H13)3/THF
For 0.20:1.Reaction is dried by high-purity chlorine purging after completing, and obtains slightly yellow solid powdery catalytic component.Its catalyst
In component: Ti%=1.14Wt%, Fe%=0.12wt%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out ethene slurry polymerization evaluation in 2L stainless steel cauldron, the consumption 50mg of catalyst,
H2/C2H4The AlEt of=0.28/0.45,1mL3Hexane solution (1mmol/mL), 1L hexane, 80 DEG C are reacted 2 hours.Urge
The synthesis condition of agent is shown in Table 1, and slurry polymerization the results are shown in Table 2.
Embodiment 3
The preparation of carbon monoxide-olefin polymeric
(1) (Grace company of the U.S. produces, and average grain diameter is 55 μm, and specific surface area is to weigh about 20g spherical silica gel
278m2/ g), silica is placed in gas-phase fluidized-bed activator, blows fluidisation with nitrogen anhydrous, anaerobic, progressively heat up
To 600 DEG C, constant temperature is dehydrated 10 hours, prepares dehydrated silica.
(2) in the reaction bulb of belt stirrer under nitrogen protection, add 100mL isopentane, (1) step will be lived through heat
Silica gel 10g after change process and the AlEt that 5.6mL concentration is 1mmol/mL3Hexane solution add, 20～30 DEG C of reactions
1 hour, heating made alkane solvent evaporate, and obtains the activated silica with mobility.
(3) in the reaction bulb of another belt stirrer, 1.74g MgCl is added2, 2,6-double [1-(2,6-dimethyl benzene imines)
Ethyl] pyridyl iron dichloride 0.3874g, 0.64mL TiCl4And 174mL oxolane, temperature rising reflux stirring 5 hours, i.e.
Prepare catalyst mother liquor.
(4) the mother liquor mixing prepared good silica gel chemically treated in (2nd) step and (3rd) step, return stirring 1 is little
When, it is then dried with high pure nitrogen purging, obtain mobility faint yellow solid powder, wherein the content of oxolane is
10.98Wt%。
(5) with isopentane as solvent under room temperature, AlEt is used2Cl and Al (n-C6H13)3Reaction to step (4) gained is produced
Thing carries out prereduction 30min, controls AlEt2The mol ratio of Cl/THF is 0.45:1, Al (n-C6H13)3/ THF is 0.20:1.
Reaction is dried by high-purity chlorine purging after completing, and obtains slightly yellow solid powdery catalytic component.In its catalytic component: Ti%
=1.27Wt%, Fe%=0.24wt%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out ethene slurry polymerization evaluation in 2L stainless steel cauldron, the consumption 50mg of catalyst,
H2/C2H4The AlEt of=0.28/0.45,1mL3Hexane solution (1mmol/mL), 1L hexane, 85 DEG C are reacted 2 hours.Urge
The synthesis condition of agent is shown in Table 1, and slurry polymerization the results are shown in Table 2.
Embodiment 4
The preparation of bimetallic catalyst composition:
(1) (Grace company of the U.S. produces, and average grain diameter is 55 μm, and specific surface area is to weigh about 20g spherical silica gel
278m2/ g), silica is placed in gas-phase fluidized-bed activator, blows fluidisation with nitrogen anhydrous, anaerobic, progressively heat up
To 600 DEG C, constant temperature is dehydrated 7 hours, prepares dehydrated silica.
(2) in the reaction bulb of belt stirrer under nitrogen protection, add 100mL isopentane, (1) step will be lived through heat
Silica gel 10g after change process and the AlEt that 5.6mL concentration is 1mmol/mL3Hexane solution add, 20 DEG C react 1
Hour, heating makes alkane solvent evaporate, and evaporating temperature is 25 DEG C, obtains the activated silica with mobility.
(3) in the reaction bulb of another belt stirrer, 1.74g MgCl is added2, 2,6-double [1-(2,6-dimethyl benzene imines)
Ethyl] pyridyl iron dichloride 0.1937g and 1.03g TiCl3And 174mL oxolane, temperature rising reflux stirs 5 hours, i.e. makes
Obtain catalyst mother liquor.
(4) the mother liquor mixing prepared good silica gel chemically treated in (2nd) step and (3rd) step, return stirring 1 is little
When, it is then dried with high pure nitrogen purging, obtain mobility faint yellow solid powder, wherein the content of oxolane is
11.8Wt%。
(5) with isopentane as solvent under room temperature, AlEt is used2Cl and Al (n-C6H13)3Reaction to step (4) gained is produced
Thing carries out prereduction, and the recovery time is 30min, controls AlEt2The mol ratio of Cl/THF is 0.45:1, Al (n-C6H13)3/THF
For 0.20:1.Reaction is dried by high-purity chlorine purging after completing, and obtains slightly yellow solid powdery catalytic component.Its catalyst
In component: Ti%=1.4Wt%, Fe%=0.12%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out ethene slurry polymerization evaluation in 2L stainless steel cauldron, the consumption 50mg of catalyst,
H2/C2H4The AlEt of=0.28/0.45,1mL3Hexane solution (1mmol/mL), 1L hexane, 80 DEG C are reacted 2 hours.Urge
Agent synthesis condition is shown in Table 1, and slurry polymerization the results are shown in Table 2.
Embodiment 5
The preparation of bimetallic catalyst composition:
(1) (Grace company of the U.S. produces, and average grain diameter is 55 μm, and specific surface area is to weigh about 20g spherical silica gel
278m2/ g), silica is placed in gas-phase fluidized-bed activator, blows fluidisation with nitrogen anhydrous, anaerobic, progressively rise
Temperature is to 600 DEG C, and constant temperature is dehydrated 4 hours, prepares dehydrated silica.
(2) in the reaction bulb of belt stirrer under nitrogen protection, add 100mL isopentane, (1) step will be lived through heat
Silica gel 10g after change process and the AlEt that 5.6mL concentration is 1mmol/mL3Hexane solution add, 25 DEG C react 4
Hour, heating makes alkane solvent evaporate, and evaporating temperature is 20 DEG C, obtains the activated silica with mobility.
(3) in the reaction bulb of another belt stirrer, 1.74g MgCl is added2, 2,6-double [1-(2,6-diisopropyl benzene imines)
Ethyl] pyridyl iron dichloride 0.1077g, 0.64mL TiCl4And 174mL oxolane, temperature rising reflux stirring 5 hours, i.e.
Prepare catalyst mother liquor.
(4) the mother liquor mixing prepared good silica gel chemically treated in (2nd) step and (3rd) step, return stirring 1 is little
When, it is then dried with high pure nitrogen purging, obtain mobility faint yellow solid powder, wherein the content of oxolane is
11.3Wt%。
(5) with isopentane as solvent under room temperature, AlEt is used2Cl and Al (n-C6H13)3Reaction to step (4) gained is produced
Thing carries out prereduction 30min, controls AlEt2The mol ratio of Cl/THF is 0.45, Al (n-C6H13)3/ THF is 0.20.Reaction
It is dried with high-purity chlorine purging after completing, obtain slightly yellow solid powdery catalytic component.In its catalytic component: Ti%=
1.27Wt%, Fe%=0.07wt%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out ethene slurry polymerization evaluation in 2L stainless steel cauldron, the consumption 50mg of catalyst,
H2/C2H4The AlEt of=0.28/0.45,1mL3Hexane solution (1mmol/mL), 1L hexane, 85 DEG C are reacted 2 hours.Urge
The synthesis condition of agent is shown in Table 1, and slurry polymerization the results are shown in Table 2.
Embodiment 6
The preparation of bimetallic catalyst composition:
(1) (Grace company of the U.S. produces, and average grain diameter is 55 μm, and specific surface area is to weigh about 20g spherical silica gel
278m2/ g), silica is placed in gas-phase fluidized-bed activator, blows fluidisation with nitrogen anhydrous, anaerobic, progressively rise
Temperature is to 600 DEG C, and constant temperature is dehydrated 10 hours, prepares dehydrated silica.
(2) in the reaction bulb of belt stirrer under nitrogen protection, add 100mL isopentane, (1) step will be lived through heat
Silica gel 10g after change process and the AlEt that 5.6mL concentration is 1mmol/mL3Hexane solution add, 30 DEG C react 4
Hour, heating makes alkane solvent evaporate, and evaporating temperature is 30 DEG C, obtains the activated silica with mobility.
(3) in the reaction bulb of another belt stirrer, 1.74g MgCl is added2, 2,6-double [1-(2,6-diisopropyl benzene imines)
Ethyl] pyridyl iron dichloride 0.2145g, 0.64mLTiCl4And 174mL oxolane, temperature rising reflux stirring 5 hours, i.e.
Prepare catalyst mother liquor.
(4) the mother liquor mixing that will be modified the silica gel handled well in (2nd) step and prepared by (3rd) step, return stirring 1 is little
When, it is then dried with high pure nitrogen purging, obtain mobility faint yellow solid powder, wherein the content of oxolane is
11.3Wt%。
(6) with isopentane as solvent under room temperature, AlEt is used2The product to step (5) gained for the Cl carries out prereduction
30min, controls AlEt2The mol ratio of Cl/THF is 0.65:1.Reaction is dried by high-purity chlorine purging after completing, and obtains micro-Huang
Look solid powdery catalytic component.In its catalytic component: Ti%=1.25Wt%, Fe%=0.11wt%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out ethene slurry polymerization evaluation in 2L stainless steel cauldron, the consumption 50mg of catalyst,
H2/C2H4The AlEt of=0.28/0.45,1mL3Hexane solution (1mmol/mL), 1L hexane, 85 DEG C are reacted 2 hours.Urge
The synthesis condition of agent is shown in Table 1, and slurry polymerization the results are shown in Table 2.
Embodiment 7
The preparation of catalytic component
(1) (Grace company of the U.S. produces, and average grain diameter is 55 μm, and specific surface area is to weigh about 20g spherical silica gel
278m2/ g), silica is placed in gas-phase fluidized-bed activator, blows fluidisation with nitrogen anhydrous, anaerobic, progressively rise
Temperature is to 600 DEG C, and constant temperature is dehydrated 8 hours, prepares dehydrated silica.
(2) in the reaction bulb of belt stirrer under nitrogen protection, add 100mL n-hexane, (1) step will be lived through heat
Change process after silica gel 10g and the hexane solution of trimethyl aluminium that 5.6mL concentration is 1mmol/mL add, 25 DEG C of reactions
4 hours, heating made alkane solvent evaporate, and evaporating temperature is 25 DEG C, obtains the activated silica with mobility.
(3) in the reaction bulb of another belt stirrer, 1.74g MgBr is added2, 2,6-double [1-(2,6-diisopropyl benzene imines)
Ethyl] pyridyl iron dichloride 0.4290g, 0.64mL TiCl4And 174mL oxolane, temperature rising reflux stirring 5 hours, i.e.
Prepare catalyst mother liquor.
(4) the mother liquor mixing that will be modified the silica gel handled well in (2nd) step and prepared by (3rd) step, return stirring 1 is little
When, it is then dried with high pure nitrogen purging, obtain mobility faint yellow solid powder, wherein the content of oxolane is
11.4Wt%。
(6) with isopentane as solvent under room temperature, Al (n-C is used6H13)3Pre-going back is carried out to the product of step (5) gained
Former 30min, controls Al (n-C6H13)3The mol ratio of/THF is 0.65, and reaction is dried by high-purity chlorine purging after completing, and obtains micro-
Yellow solid powder catalyst component.In its catalytic component: Ti%=1.25Wt%, Fe%=0.22wt%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out ethene slurry polymerization evaluation in 2L stainless steel cauldron, the consumption 50mg of catalyst,
H2/C2H4The AlEt of=0.28/0.45,1mL3Hexane solution (1mmol/mL), 1L hexane, 85 DEG C are reacted 2 hours.Urge
The synthesis condition of agent is shown in Table 1, and slurry polymerization the results are shown in Table 2.
Embodiment 8
The preparation of bimetallic catalyst composition:
(1) (Grace company of the U.S. produces, and average grain diameter is 55 μm, and specific surface area is to weigh about 20g spherical silica gel
278m2/ g), silica is placed in gas-phase fluidized-bed activator, blows fluidisation with nitrogen anhydrous, anaerobic, progressively rise
Temperature is to 200 DEG C, and constant temperature is dehydrated 8 hours, prepares dehydrated silica.
(2) in the reaction bulb of belt stirrer under nitrogen protection, add 100mL normal heptane, (1) step will be lived through heat
Change process after silica gel 10g and the hexane solution of tri-n-hexyl aluminum that 5.6mL concentration is 1mmol/mL add, anti-at 25 DEG C
Answering 4 hours, heating makes alkane solvent evaporate, and evaporating temperature is 30 DEG C, obtains the activated silica with mobility.
(3) in the reaction bulb of another belt stirrer, 1.74g MgI is added2, 2,6-double [1-(2,6-dimethyl benzene imines) second
Base] pyridyl iron dichloride 0.2145g and 1.03g TiCl3And 174mL oxolane, temperature rising reflux stirs 5 hours, i.e. prepared
Catalyst mother liquor.
(4) the mother liquor mixing prepared good silica gel chemically treated in (2nd) step and (3rd) step, return stirring 1 is little
When, it is then dried with high pure nitrogen purging, obtain mobility faint yellow solid powder, wherein the content of oxolane is
11.1Wt%。
(5) with isopentane as solvent under room temperature, AlEt is used2Cl and Al (n-C6H13)3Reaction to step (5) gained is produced
Thing carries out prereduction 30min, controls AlEt2The mol ratio of Cl/THF is 0.45:1, Al (n-C6H13)3/ THF is 0.20:1.
Reaction is dried by high-purity chlorine purging after completing, and obtains slightly yellow solid powdery catalytic component.In its catalytic component: Ti%
=1.46Wt%, Fe%=0.11wt%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out ethene slurry polymerization evaluation in 2L stainless steel cauldron, the consumption 50mg of catalyst,
H2/C2H4The AlEt of=0.28/0.45,1mL3Hexane solution (1mmol/mL), 1L hexane, 85 DEG C are reacted 2 hours.Urge
The synthesis condition of agent is shown in Table 1, and slurry polymerization the results are shown in Table 2.
Comparative example 1
The preparation of bimetallic catalyst composition:
(1) (Grace company of the U.S. produces, and average grain diameter is 55 μm, and specific surface area is to weigh about 20g spherical silica gel
278m2/ g), silica is placed in gas-phase fluidized-bed activator, blows fluidisation with nitrogen anhydrous, anaerobic, progressively rise
Temperature is to 200 DEG C, and constant temperature is dehydrated 8 hours, prepares dehydrated silica.
(2) in the reaction bulb of belt stirrer under nitrogen protection, add 100mL normal heptane, (1) step will be lived through heat
Change process after silica gel 10g and the hexane solution of tri-n-hexyl aluminum that 5.6mL concentration is 1mmol/mL add, anti-at 25 DEG C
Answering 4 hours, heating makes alkane solvent evaporate, and evaporating temperature is 30 DEG C, obtains the activated silica with mobility.
(3) in the reaction bulb of another belt stirrer, 1.74g MgCl is added2、0.64mL TiCl4And 174mL tetrahydrochysene furan
Muttering oxolane, temperature rising reflux stirs 5 hours, i.e. prepares catalyst mother liquor.
(4) the mother liquor mixing prepared good silica gel chemically treated in (2nd) step and (3rd) step, return stirring 1 is little
When, it is then dried with high pure nitrogen purging, obtain mobility faint yellow solid powder, wherein the content of oxolane is
10.9Wt%。
(5) with isopentane as solvent under room temperature, AlEt is used2Cl and Al (n-C6H13)3Reaction to step (5) gained is produced
Thing carries out prereduction 30min, controls AlEt2The mol ratio of Cl/THF is 0.45:1, Al (n-C6H13)3/ THF is 0.20:1.
Reaction is dried by high-purity chlorine purging after completing, and obtains slightly yellow solid powdery catalytic component.In its catalytic component: Ti%
=1.20Wt%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out ethene slurry polymerization evaluation in 2L stainless steel cauldron, the consumption 50mg of catalyst,
H2/C2H4The AlEt of=0.28/0.45,1mL3Hexane solution (1mmol/mL), 1L hexane, 85 DEG C are reacted 2 hours.Urge
The synthesis condition of agent is shown in Table 1, and slurry polymerization the results are shown in Table 2.
Comparative example 2
The preparation of bimetallic catalyst composition:
(1) (Grace company of the U.S. produces, and average grain diameter is 55 μm, and specific surface area is to weigh about 20g spherical silica gel
278m2/ g), silica is placed in gas-phase fluidized-bed activator, blows fluidisation with nitrogen anhydrous, anaerobic, progressively rise
Temperature is to 600 DEG C, and constant temperature is dehydrated 10 hours, prepares dehydrated silica.
(2) in the reaction bulb of belt stirrer under nitrogen protection, add 100mL isopentane, (1) step will be lived through heat
Silica gel 10g after change process and the AlEt that 5.6mL concentration is 1mmol/mL3Hexane solution add, 30 DEG C react 4
Hour, heating makes alkane solvent evaporate, and evaporating temperature is 30 DEG C, obtains the activated silica with mobility.
(3) in the reaction bulb of another belt stirrer, 1.74g MgCl is added2, 2,6-double [1-(2,6-diisopropyl benzene imines)
Ethyl] pyridyl iron dichloride 0.2145g and 174mL oxolane, temperature rising reflux stirs 5 hours, i.e. prepares catalyst mother liquor.
(4) the mother liquor mixing that will be modified the silica gel handled well in (2nd) step and prepared by (3rd) step, return stirring 1 is little
When, it is then dried with high pure nitrogen purging, obtain mobility faint yellow solid powder, wherein the content of oxolane is
11.5Wt%。
(6) with isopentane as solvent under room temperature, AlEt is used2The product to step (5) gained for the Cl carries out prereduction
30min, controls AlEt2The mol ratio of Cl/THF is 0.65:1.Reaction is dried by high-purity chlorine purging after completing, and obtains micro-Huang
Look solid powdery catalytic component.In its catalytic component: Fe%=0.11wt%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out ethene slurry polymerization evaluation in 2L stainless steel cauldron, the consumption 50mg of catalyst,
H2/C2H4The AlEt of=0.28/0.45,1mL3Hexane solution (1mmol/mL), 1L hexane, 85 DEG C are reacted 2 hours.Urge
The synthesis condition of agent is shown in Table 1, and slurry polymerization the results are shown in Table 2.
The synthesis condition of table 1 catalyst
Table 2 slurry lab scale evaluation result
Claims (10)
1. the preparation method of an ethene gas-phase polymerization or copolymerization catalyst composition, it is characterised in that: comprise the steps:
(1) being dissolved in titanium compound, iron compound and magnesium compound in oxolane, making mother liquor, wherein titanium compound, iron compound joined in oxolane before or after magnesium compound；The weight of titanium compound and iron compound is than for 1000:1～1:1；The weight of magnesium compound and iron compound is than for 100:1～1:1；The weight of oxolane and iron compound is than for 10000:1～1:1；
(2) will join in mother liquor prepared by (1) step through the chemically treated modified silica support of Overheating Treatment and alkyl aluminum, return stirring 1 hour, afterwards it is dried by high pure nitrogen purging, the excessive oxolane of removing, the residue content of control oxolane accounts for 10～15wt% of products therefrom gross weight；
(3) solids that step (2) is obtained, being suspended in lower paraffin hydrocarbon solvent, at room temperature carrying out reduction treatment with one or more alkyl aluminum compounds, the reduction treatment time is 30min, it is dried with high pure nitrogen purging, prepare described carbon monoxide-olefin polymeric again.
2. the preparation method of ethene gas-phase polymerization according to claim 1 or copolymerization catalyst composition, it is characterised in that:
Described lower paraffin hydrocarbon solvent is pentane or hexane.
3. the preparation method of ethene gas-phase polymerization according to claim 1 or copolymerization catalyst composition, it is characterised in that:
Through the chemically treated silica supports of Overheating Treatment and alkyl aluminum be spherical or class is spherical, and its average grain diameter is 10～100 μm, specific surface area 250～800m2/g；Silica is processed as follows:
A. being placed in silica in gas-phase fluidized-bed activator, blowing fluidisation with nitrogen anhydrous, anaerobic, be progressively warming up to 200～700 DEG C, constant temperature is dehydrated 4～10 hours, prepares dehydrated silica；
B. adding alkane solvent in dehydrated silica, the addition of solvent is 10mL/g SiO2And add alkyl metal cpd to process the hydroxyl on surface, described alkyl metal cpd is alkyl aluminum, the weight ratio of its consumption is: A1/Si is 0.05～0.1:1, stir 1～4 hour under room temperature, heating makes alkane solvent evaporate, and the temperature of evaporation is 20～30 DEG C, obtains the activated silica with mobility.
4. the preparation method of the ethene gas-phase polymerization according to claim l or copolymerization catalyst composition, it is characterised in that: described magnesium compound is MgCl2、MgBr2、MgI2Or its mixture.
5. the preparation method of ethene gas-phase polymerization according to claim 1 or copolymerization catalyst composition, it is characterised in that: described titanium compound is Ti (OR)4-nXnOr TiX3, in formula, R is C1～C3Aliphatic group, X is one or more of F, Cl, Br, and n is the integer of 1～4.
6. the preparation method of ethene gas-phase polymerization according to claim 1 or copolymerization catalyst composition, it is characterised in that: the structure of wherein said iron containing compounds shown in formula I:
The structure of I late transition metal complex
Wherein: R1～R3For alkyl, alkoxyl, phenoxy group, benzyl, halogen；M is Fe.
7. the preparation method of ethene gas-phase polymerization according to claim 1 or copolymerization catalyst composition, it is characterised in that: the formula of described alkyl aluminum compound is AlRmX3-m, R is C that is identical or that differ1-8Alkyl, X is halogen, and m is the integer of 1～3.
8. the preparation method of ethene gas-phase polymerization according to claim 1 or copolymerization catalyst composition, it is characterised in that: described alkyl aluminum compound is AlEt3、Al(iso-Bu)3、Al(n-C6H13)3、Al(n-C8H17)3、AlEt2The mixture of one or more in Cl.
9. an ethene gas-phase polymerization or copolymerization catalyst composition, it is characterised in that: it is prepared by the preparation method of ethene gas-phase polymerization according to claim 1 or copolymerization catalyst composition.
10. the application of the ethene gas-phase polymerization described in a claim 9 or copolymerization catalyst composition, it is characterised in that: described carbon monoxide-olefin polymeric forms the copolymerization catalyst for ethylene homo conjunction or ethene and other alpha-olefins for the complex catalyst system together with co-catalyst alkyl aluminum compound.
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| WO2001023444A1 (en) * | 1999-09-29 | 2001-04-05 | E.I. Du Pont De Nemours And Company | Polymerization of olefins with bimetallic polymerisation catalyst system |
| CN1493404A (en) * | 2002-10-29 | 2004-05-05 | 中国科学院化学研究所 | Carrier bifunction catalyst and its preparation method and application |
| CN1667001A (en) * | 2004-03-10 | 2005-09-14 | 中国石油化工股份有限公司 | Compound catalyst for olefin polymerization |
| CN101044171A (en) * | 2004-10-21 | 2007-09-26 | 托塔尔石油化学产品研究弗吕公司 | Polyolefins prepared from a metallocene and a new single site catalyst components in a single reactor |
| CN101235110A (en) * | 2008-01-14 | 2008-08-06 | 中国石油天然气股份有限公司大庆化工研究中心 | Ethene gas-phase polymerization or copolymerization catalyst composition and preparation method thereof |
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| WO2001023444A1 (en) * | 1999-09-29 | 2001-04-05 | E.I. Du Pont De Nemours And Company | Polymerization of olefins with bimetallic polymerisation catalyst system |
| CN1493404A (en) * | 2002-10-29 | 2004-05-05 | 中国科学院化学研究所 | Carrier bifunction catalyst and its preparation method and application |
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| CN101044171A (en) * | 2004-10-21 | 2007-09-26 | 托塔尔石油化学产品研究弗吕公司 | Polyolefins prepared from a metallocene and a new single site catalyst components in a single reactor |
| CN101235110A (en) * | 2008-01-14 | 2008-08-06 | 中国石油天然气股份有限公司大庆化工研究中心 | Ethene gas-phase polymerization or copolymerization catalyst composition and preparation method thereof |
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